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WO2013176101A1 - Lactic acid production method - Google Patents

Lactic acid production method Download PDF

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Publication number
WO2013176101A1
WO2013176101A1 PCT/JP2013/064004 JP2013064004W WO2013176101A1 WO 2013176101 A1 WO2013176101 A1 WO 2013176101A1 JP 2013064004 W JP2013064004 W JP 2013064004W WO 2013176101 A1 WO2013176101 A1 WO 2013176101A1
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WO
WIPO (PCT)
Prior art keywords
lactic acid
glycerol
ion exchange
exchange resin
aqueous solution
Prior art date
Application number
PCT/JP2013/064004
Other languages
French (fr)
Japanese (ja)
Inventor
河村　健司
正照 伊藤
山田　勝成
Original Assignee
東レ株式会社
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Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to BR112014027543-2A priority Critical patent/BR112014027543B1/en
Priority to EP13793821.3A priority patent/EP2853525B1/en
Priority to CN201380026696.9A priority patent/CN104334520B/en
Priority to JP2013535974A priority patent/JP6260277B2/en
Priority to RU2014151793A priority patent/RU2643147C2/en
Priority to US14/399,992 priority patent/US10072117B2/en
Priority to ES13793821T priority patent/ES2792128T3/en
Publication of WO2013176101A1 publication Critical patent/WO2013176101A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/08—Lactic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/56—Lactic acid

Definitions

  • the present invention relates to a method for producing lactic acid by separating lactic acid and glycerol in an aqueous lactic acid solution.
  • Lactic acid is widely applied to industrial uses as a monomer raw material for biodegradable plastics, in addition to uses such as food and medicine, and the demand is increasing.
  • 2-Hydroxypropionic acid that is, lactic acid
  • lactic acid is known to be produced by fermentation by microorganisms, and microorganisms convert a substrate containing a carbohydrate represented by glucose into lactic acid.
  • Lactic acid is classified into (L) -isomer and (D) -isomer optical isomers depending on the conformation of the substituent bonded to the carbon at the carbonyl ⁇ -position.
  • lactic acid is selectively selected or a mixture of (L) -form and (D) -form (racemic form).
  • lactic acid is selectively selected or a mixture of (L) -form and (D) -form (racemic form).
  • lactic acid by microbial fermentation is performed while maintaining an optimum pH for microbial fermentation by adding an alkaline substance (for example, calcium hydroxide) to the culture solution.
  • alkaline substance for example, calcium hydroxide
  • lactate salt for example, calcium lactate
  • lactic acid fermentation broth obtained by microbial fermentation in addition to the target lactic acid, in addition to organic acids and their salts, proteins, amino acids, nonionic compounds such as glycerol are included as impurities, When lactic acid is used as a plastic monomer, it is necessary to separate lactic acid from these impurities.
  • Patent Document 1 discloses an ion exchange treatment of an aqueous lactic acid solution to remove ionic components, A method of distillation is described. Further, as a method for removing nonionic impurities, Patent Document 2 discloses a method for removing glycerol, which is an impurity contained in an aqueous lactic acid solution, by adsorbing and eluting lactic acid contained in the aqueous lactic acid solution to an ion exchange resin. (However, the example of Patent Document 2 does not describe an example in which lactic acid is adsorbed and eluted in an ion exchange resin.).
  • glycerol contained in the aqueous lactic acid solution is adsorbed and eluted by an ion exchange resin, thereby removing glycerol as an impurity.
  • an ion exchange resin in order to adsorb a large amount of lactic acid on the ion exchange resin, a large amount of ion exchange resin is required, and thus problems such as an increase in equipment size have been considered.
  • an object of the present invention is to provide a method for producing lactic acid with reduced glycerol easily and at low cost when separating lactic acid from an aqueous lactic acid solution containing glycerol as an impurity.
  • glycerol which is a nonionic impurity contained in an aqueous lactic acid solution, can be adsorbed on an ion exchange resin, and complete the present invention. It came to.
  • the present invention comprises the following (1) to (6).
  • a method for producing lactic acid comprising a step of removing glycerol from an aqueous lactic acid solution containing glycerol as an impurity by an ion exchange resin.
  • glycerol contained as an impurity in an aqueous lactic acid solution can be reduced efficiently and at low cost by a simple operation, and lactic acid suitable for producing polylactic acid having an excellent melting point and thermal stability is produced. It becomes possible to do.
  • the method for producing lactic acid according to the present invention includes a step of removing glycerol from an aqueous lactic acid solution containing glycerol as an impurity by an ion exchange resin.
  • an aqueous lactic acid solution containing glycerol as an impurity means an aqueous solution containing lactic acid as a main component and glycerol as an impurity.
  • the origin of the lactic acid aqueous solution is not particularly limited as long as it contains glycerol as an impurity, and may be an aqueous solution of lactic acid obtained by organic synthesis, from the lactic acid fermentation broth itself obtained by microbial fermentation, or from the lactic acid fermentation broth It may have undergone a plurality of separation and purification steps.
  • lactic acid is an ionic substance
  • lactic acid in lactic acid aqueous solution containing glycerol as an impurity, lactic acid may exist as free lactic acid, may exist as lactate salt, or they may be in an equilibrium state.
  • the glycerol removal effect according to the present invention is high when lactic acid is present in a free form.
  • the lactic acid and glycerol contained in the lactic acid aqueous solution can be quantified by high performance liquid chromatography (HPLC).
  • the glycerol contained in the lactic acid aqueous solution is adsorbed on the ion exchange resin.
  • An ion exchange resin is a kind of synthetic resin and has a structure that ionizes as an ionic group in a part of its molecular structure, and thus exhibits an ion exchange action with an ion component in a solvent.
  • ion exchange resins are generally used for the purpose of adsorbing ionic components in solution, but glycerol, which is a nonionic component in a highly polar solution such as an aqueous lactic acid solution, is found adsorbed on ion exchange resins.
  • glycerol which is a nonionic component in a highly polar solution such as an aqueous lactic acid solution, is found adsorbed on ion exchange resins.
  • the ion exchange resin used in the present invention is not particularly limited, and generally known ion exchange resins can be used. Specific examples include “Amberlite” (registered trademark) (manufactured by Dow Chemical Co.), “Diaion” (registered) Trademark) (manufactured by Mitsubishi Chemical Corporation), “Duolite” (registered trademark) (manufactured by Rohm and Haas), and the like are commercially available.
  • the ion exchange resin may be acidic (cation exchange resin), basic (anion exchange resin), or a salt form thereof, but a strong acid ion exchange resin is preferable because of its excellent glycerol adsorption ability, and H type. The strongly acidic ion exchange resin is particularly preferable.
  • ion exchange resins can be used in either a so-called gel type or porous type resin.
  • strongly acidic ion exchange resins include “Diaion” (registered trademark) SK1B, SK1BH, SK110, SK112, PK216, PK216H, PK218, PK220, PK228, PK228H, UBK08, UBK10, UBK12 manufactured by Mitsubishi Chemical Corporation.
  • a method of bringing the aqueous lactic acid solution into contact with the ion exchange resin either a batch method (stirring tank method) or a column method (fixed bed flow method) can be adopted. Is preferred.
  • the flow rate of the aqueous lactic acid solution in the case of ion exchange treatment using an ion exchange resin column is not particularly limited, but it is usually set so that the space velocity (SV) per unit volume of the ion exchange resin is 0.1 to 20 hr ⁇ 1. That's fine.
  • the contact temperature between the ion exchange resin column and the lactic acid aqueous solution is not particularly limited and can be suitably used at room temperature.
  • the ion exchange resin used for glycerol removal can be regenerated by washing with water.
  • regeneration of ion exchange resins that adsorb ionic components requires washing with chemicals such as acid and alkali, but ion exchange resins that adsorb glycerol, which is a nonionic component, can be regenerated by washing with highly polar water. Therefore, the chemical cost required for ion exchange resin regeneration can be reduced.
  • the water used for resin regeneration is not particularly limited, but when water containing a large amount of ionic components is used, the ionic components are adsorbed on the functional groups on the surface of the ion exchange resin by the ionic components, and the glycerol adsorption effect is reduced.
  • washing with ion-exchanged water can be preferably applied.
  • the aqueous lactic acid solution used for the ion exchange resin process is a lactic acid fermentation broth by microbial fermentation
  • an alkaline substance is generally added to adjust the pH during the cultivation, so lactic acid in the lactic acid fermentation broth exists as a lactate. To do.
  • Specific examples of the lactate include lithium lactate, sodium lactate, potassium lactate, calcium lactate, magnesium lactate, aluminum lactate, ammonium lactate, and mixtures thereof.
  • the functional groups on the surface of the ion exchange resin are preferentially used to make the lactate free lactic acid, thereby reducing the glycerol adsorption effect. Therefore, the effect of removing glycerol can be enhanced by treating an aqueous solution of lactic acid that has been made free in advance with an ion exchange resin.
  • an acidic substance As a method for obtaining free lactic acid from lactate, a method of adding an acidic substance can be employed.
  • the acidic substance is not particularly limited, and sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid, nitric acid and the like can be used, but sulfuric acid is preferably used from the viewpoint of forming a hardly soluble salt described later. It is preferable to add an acidic substance to the aqueous lactate solution to convert it into a free lactic acid aqueous solution, and to remove the cationic component of the lactate as a hardly soluble salt.
  • the method for solid-liquid separation of the hardly soluble salt is not particularly limited, and methods known to those skilled in the art, such as filtration with qualitative filter paper and centrifugation, can be applied.
  • the aqueous lactic acid solution may be subjected to a step of removing dissolved salts.
  • the glycerol adsorption effect in the ion exchange resin process can be enhanced.
  • the method for removing the dissolved salt in the lactic acid aqueous solution and ion exchange treatment, membrane filtration treatment, and the like are applied.
  • the ion exchange treatment here is to remove ionic components (inorganic salts, etc.) in the lactic acid aqueous solution, and to remove glycerol which is an impurity of the lactic acid aqueous solution with the ion exchange resin in the present invention.
  • the purpose is different.
  • the membrane filtration treatment is not particularly limited as long as it is a membrane that permeates lactic acid and blocks salts, but a nanofiltration membrane is preferable.
  • the nanofiltration membrane is also called a nanofilter (nanofiltration membrane, NF membrane), and is a membrane generally defined as “a membrane that transmits monovalent ions and blocks divalent ions”. . It is a membrane that is considered to have a minute gap of about several nanometers, and is mainly used to block minute particles, molecules, ions, salts, and the like in water.
  • the material of the nanofiltration membrane can be a polymer material such as cellulose acetate polymer, polyamide, polyester, polyimide, vinyl polymer, but is not limited to the membrane composed of the one kind of material.
  • membrane raw materials may be sufficient.
  • the membrane structure has a dense layer on at least one side of the membrane, and on the asymmetric membrane having fine pores gradually increasing from the dense layer to the inside of the membrane or the other side, or on the dense layer of the asymmetric membrane.
  • a composite film having a very thin functional layer formed of another material may be used.
  • the composite membrane for example, a composite membrane described in JP-A-62-201606 in which a nanofiltration membrane comprising a functional layer of polyamide is formed on a support membrane made of polysulfone as a membrane material can be used.
  • the nanofiltration membrane is generally used as a spiral membrane element, but the nanofiltration membrane used in the present invention is also preferably used as a spiral membrane element.
  • Specific examples of preferred nanofiltration membrane elements include “GEsepa” (registered trademark) manufactured by GE Osmonics, NF99 or NF99HF manufactured by Alfa Laval, NF-45, NF-90, NF-200 manufactured by Filmtech. NF-400, Nanofiltration membrane element SU-210, SU-220, SU-600 or SU-610 manufactured by Toray Industries Inc., including UTC60.
  • the lactic acid concentration of the aqueous lactic acid solution used in the ion exchange resin process is not particularly limited. However, when the lactic acid concentration of the aqueous lactic acid solution is less than 20% by weight, the glycerol adsorption of the ion exchange resin is caused by the influence of highly polar water. Therefore, it is preferable to treat with an ion exchange resin after concentrating the lactic acid concentration to 20% by weight or more by a concentration operation. In addition, when the lactic acid concentration of the lactic acid aqueous solution exceeds 90% by weight, the viscosity of the lactic acid aqueous solution becomes high, and the fluidity and operability of the lactic acid aqueous solution in the ion exchange resin process are lowered. It is preferable to treat with an ion exchange resin.
  • the method of concentrating the lactic acid aqueous solution can evaporate water by heating and decompression with a concentrating device typified by an evaporator, or increase the lactic acid concentration by a reverse osmosis membrane, but can reduce the energy required for concentration.
  • a concentration method using a reverse osmosis membrane is preferred.
  • the reverse osmosis membrane here is a filtration membrane capable of filtering out ions and low molecular weight molecules by using a pressure difference equal to or higher than the osmotic pressure of non-treated water as a driving force.
  • the water in the lactic acid aqueous solution is allowed to permeate through the permeation side of the reverse osmosis membrane, thereby obtaining the lactic acid aqueous solution having an increased lactic acid concentration on the non-permeation side.
  • the membrane material of the reverse osmosis membrane for concentration of the lactic acid aqueous solution commercially available polymer materials such as cellulose acetate polymer, polyamide, polyester, polyimide, vinyl polymer can be used. It is not limited to the film
  • the membrane structure has a dense layer on at least one side of the membrane, and on the asymmetric membrane having fine pores gradually increasing from the dense layer to the inside of the membrane or the other side, or on the dense layer of the asymmetric membrane. Either a composite film having a very thin functional layer formed of another material may be used.
  • a membrane form of a reverse osmosis membrane the thing of appropriate forms, such as a flat membrane type, a spiral type, and a hollow fiber type, can be used.
  • reverse osmosis membrane examples include polyamide reverse osmosis membrane UTC-70, SU-710, SU-720, SU-720F, SU-710L, SU-720L, SU-720LF, SU-720R manufactured by Toray Industries, Inc. , SU-710P, SU-720P, SU-810, SU-820, SU-820L, SU-820FA, SU-610, SU-620, TM800, TM800C, TM800A, TM800H, TM800E, TM800L, manufactured by Toray Industries, Inc.
  • the lactic acid aqueous solution obtained in the ion exchange resin step is further subjected to a distillation step, whereby high-purity lactic acid with further reduced glycerol can be obtained.
  • a distillation step whereby high-purity lactic acid with further reduced glycerol can be obtained.
  • the lactic acid concentration of the aqueous lactic acid solution used for the distillation process and the lactic acid aqueous solution obtained by the ion exchange resin treatment may be distilled as it is, and further subjected to the concentration step using an evaporator or the above-mentioned reverse osmosis membrane before the distillation. May be.
  • distillation can be suitably performed.
  • the distillation step is performed under a reduced pressure of 1 Pa or more and atmospheric pressure (normal pressure, about 101 kPa) or less. It is more preferable to carry out under a reduced pressure of 10 Pa or more and 30 kPa or less because the distillation temperature can be reduced.
  • the distillation temperature under reduced pressure is 20 ° C. or higher and 200 ° C. or lower. However, when distillation is performed at 180 ° C.
  • lactic acid may be racemized due to the influence of impurities.
  • the lactic acid can be suitably distilled at a temperature of °C or lower, more preferably 60 °C or higher and 150 °C or lower.
  • lactic acid is structurally easy to oligomerize under dehydrating conditions (heating, reduced pressure), and therefore it is preferable to reduce the residence time as much as possible. Therefore, since a short-time distillation can be achieved by using a thin film evaporator such as a falling film evaporator or a wiping film evaporator as the distillation apparatus, it is preferable because the recovery rate of lactic acid can be improved.
  • the polylactic acid obtained by polymerizing lactic acid is composed of homopolymers of L-lactic acid units or D-lactic acid units, segments composed of poly-L-lactic acid units, and segments composed of poly-D-lactic acid units.
  • Polylactic acid block copolymers and copolymers with other monomers other than lactic acid are included.
  • monomer units other than lactic acid include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neo Glycol compounds such as pentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid Acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxypheny
  • the method for producing the polylactic acid is not particularly limited, and a general method for producing polylactic acid can be used. Specifically, a lactide which is a cyclic dimer is produced once using lactic acid as a raw material, and then ring-opening polymerization is performed, and a direct dehydration polycondensation of the raw material in a solvent is performed. A direct polymerization method in stages is known, and any production method may be used.
  • the polymerization time can be shortened by using a catalyst for the polymerization reaction.
  • the catalyst include metals such as tin, zinc, lead, titanium, bismuth, zirconium, germanium, antimony, and aluminum, and derivatives thereof. Derivatives are preferably metal alkoxides, carboxylates, carbonates, oxides and halides. Specific examples include tin chloride, tin acetate, tin octylate, zinc chloride, lead oxide, lead carbonate, titanium chloride, alkoxytitanium, germanium oxide, zirconium oxide, etc. Among these, tin compounds are preferred, and tin acetate Or tin octylate is more preferable.
  • the polymerization reaction can be usually performed at a temperature of 100 to 200 ° C. in the presence of the above catalyst, although it varies depending on the catalyst type. Moreover, in order to remove the water produced
  • a compound containing two or more hydroxyl groups or amino groups in the molecule may be used as the polymerization initiator.
  • the compound containing two or more hydroxyl groups or amino groups in the molecule as a polymerization initiator ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, neopentyl glycol, diethylene glycol, triethylene glycol
  • Polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, poly (vinyl alcohol), poly (hydroxyethyl methacrylate), poly (hydroxypropyl methacrylate), Ethylenediamine, propylenediamine, butanediamine, hexanediamine, diethylene
  • the amount of the polymerization initiator to be added is not particularly limited, but is 0.1% with respect to 100 parts by weight of the raw material used (L-lactic acid, D-lactic acid, L, L-lactide or D, D-lactide). 001 to 5 parts by weight is preferable, and 0.01 to 3 parts by weight is more preferable.
  • the solvent used when producing polylactic acid by the direct polymerization method is not particularly limited as long as it does not affect the polymerization, and water or an organic solvent can be used.
  • an organic solvent for example, aromatic hydrocarbons can be mentioned. Examples of aromatic hydrocarbons include toluene, xylene, naphthalene, chlorobenzene, diphenyl ether, and the like.
  • polymerization can be accelerated
  • Examples 1 to 4 Adsorption / removal test of glycerol with ion exchange resin
  • lactic acid aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • 350 g of pure water was added to prepare a 20% by weight lactic acid aqueous solution at 120 ° C.
  • the mixture was heated and refluxed in an oil bath for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution to obtain an aqueous solution of lactic acid monomer.
  • glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol.
  • 20 g of this aqueous lactic acid solution is 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) (Example 1), Na-type strongly acidic ion exchange resin “Diaion” ( (Registered trademark) SK1B (manufactured by Mitsubishi Chemical Corporation) 2 g (Example 2), CL type strongly basic ion exchange resin “Amberlite” (registered trademark) IR410JCL (manufactured by Dow Chemical Co.) 2 g (Example 3), OH Type weakly basic ion exchange resin “Diaion” (registered trademark) WA20 (Mitsubishi Chemical Corporation) 2 g (Example 4) was added and stirred at room temperature for 2 hours at 300 rpm.
  • H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) Example 1
  • the glycerol concentration in the aqueous lactic acid solution before and after the ion exchange resin treatment was measured by high performance liquid chromatography, and the glycerol adsorption removal rate was calculated by the method of the following formula 1.
  • Glycerol adsorption removal rate (%) 100 ⁇ (glycerol concentration before ion exchange resin treatment (g / L) ⁇ glycerol concentration after ion exchange resin treatment (g / L)) / glycerol concentration before ion exchange resin treatment (g / L) (Formula 1).
  • the glycerol concentration in the aqueous lactic acid solution was measured under the following conditions by high performance liquid chromatography (manufactured by Shimadzu Corporation). The results are shown in Table 1.
  • Column: ShodexNH2P-50 4E (manufactured by Showa Denko KK), mobile phase: acetonitrile: water 3: 1, flow rate: 0.6 mL / min, detection method: differential refractive index detector (RI), column temperature: 30 ° C.
  • glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol.
  • 0.1 g of activated carbon Shirasagi A manufactured by Nippon Enviro Chemicals
  • qualitative filter paper No. The activated carbon was filtered off with No. 2 (manufactured by Advantech) to obtain an activated lactic acid aqueous solution.
  • the glycerol adsorption removal rate by the activated carbon treatment was calculated in the same procedure as in Examples 1 to 4. The results are shown in Table 1.
  • a lactic acid aqueous solution with reduced glycerol can be obtained by treating a lactic acid aqueous solution containing glycerol with an ion exchange resin, and that a strong acidic ion exchange resin has a particularly high glycerol removal effect. all right.
  • Lactic acid concentration dependency test in glycerol removal by ion exchange resin 90% by weight of lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 100 g pure water 345.5 g, glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) 4.5 g was added to prepare a 20% by weight aqueous lactic acid solution (concentration of glycerol lactate of 5% by weight), and heated to reflux in an oil bath at 120 ° C. for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution. An aqueous solution was obtained.
  • Example 5 90% by weight (Example 5), 75% by weight (Example 6), 50% by weight (Example 7), 25% by weight (Example 8), and 10% by weight of an aqueous lactic acid solution using a rotary evaporator.
  • Example 9 Concentrate to (Example 9). 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) was added to 20 g of each concentration of lactic acid aqueous solution, followed by stirring at 300 rpm for 2 hours at room temperature. The glycerol removal rate in each sample was calculated in the same manner as in Examples 1 to 4. The results are as shown in Table 2. It was shown that the higher the lactic acid concentration, that is, the lower the water concentration, the higher the glycerol adsorption removal effect.
  • Example 10 Glycerol removal test using ion exchange resin regenerated with ion-exchanged water 1050 g of pure water was added to 300 g of 90% by weight lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 20% by weight lactic acid aqueous solution. The mixture was heated and refluxed in an oil bath at 5 ° C. for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution to obtain an aqueous solution of the lactic acid monomer.
  • lactic acid aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol.
  • 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) was added to 200 g of this aqueous lactic acid solution, and the mixture was stirred at 300 rpm for 2 hours at room temperature.
  • the ion exchange resin was separated by suction filtration to obtain an ion exchange resin adsorbed with glycerol.
  • Example 10 From the results of Example 10 and Reference Example 1, it was shown that the ion exchange resin can be regenerated by washing the ion exchange resin adsorbed with glycerol with ion exchange water.
  • Reference Example 2 Production of lactic acid by batch fermentation
  • the most typical batch fermentation was performed as a fermentation form using microorganisms, and the lactic acid productivity was evaluated.
  • a batch fermentation test was conducted using the lactic acid fermentation medium shown in Table 1. The medium was used after autoclaving (121 ° C., 15 minutes).
  • the L-lactic acid fermenting yeast strain SW-1 described in WO2009 / 004922 was used as a microorganism, and the concentration of lactic acid as a product was evaluated using the HPLC shown below.
  • Reference Example 2 The operating conditions of Reference Example 2 are shown below. Reaction tank capacity (lactic acid fermentation medium amount): 2 (L), temperature adjustment: 30 (° C.), reaction tank aeration rate: 0.2 (L / min), reaction tank stirring speed: 400 (rpm), pH adjustment: Adjust to pH 5 with 1N calcium hydroxide.
  • the SW-1 strain was cultured overnight in a test tube with 5 ml of lactic acid fermentation medium (pre-culture).
  • the culture solution was inoculated into 100 ml of fresh lactic acid fermentation medium and cultured with shaking in a 500 ml Sakaguchi flask for 24 hours (pre-culture). Temperature adjustment and pH adjustment were performed, and fermentation culture was performed. The amount of bacterial cell growth at this time was 15 in terms of absorbance at 600 nm.
  • the resulting lactic acid fermentation broth (lactic acid concentration 30 g / L, glycerol concentration 1 g / L) was used in the following examples.
  • Example 11 Example of production of lactic acid using lactic acid fermentation broth as raw material (Acquisition of free lactic acid by addition of acidic substance) Concentrated sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to pH 2.5 while stirring 40 L of the culture solution obtained in Reference Example 2, and the precipitated calcium sulfate was added to qualitative filter paper No. 2 (manufactured by Advantech), and the filtrate was recovered.
  • Concentrated sulfuric acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the nanofiltration membrane permeate is concentrated using a reverse osmosis membrane module SU-810 (manufactured by Toray Industries, Inc.), and the water is evaporated under reduced pressure (50 hPa) using a rotary evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.). And concentrated to obtain a 75% aqueous lactic acid solution.
  • the concentration of glycerol was analyzed by high performance liquid chromatography in the same manner as in Example 1. As a result, the glycerol concentration relative to lactic acid was 2.0% by weight.
  • lactic acid aqueous solution treated with an ion exchange resin was distilled under reduced pressure at 133 Pa and 130 ° C. to obtain 156 g of lactic acid. Pure water was added to the obtained lactic acid to prepare a 90 wt% lactic acid aqueous solution.
  • the glycerol concentration in the 90% by weight lactic acid aqueous solution was measured using “F-kit glycerol” (manufactured by Roche Diagnostics). As a result, the glycerol content in the 90% by weight lactic acid aqueous solution was 17 ppm.
  • Lactic acid production example using lactic acid fermentation broth as raw material Lactic acid was produced in the same procedure as in Example 11 except that glycerol was not removed by adsorption by ion exchange resin treatment. Got. Water was added to the obtained lactic acid to prepare a 90% by weight aqueous lactic acid solution. The glycerol concentration in the 90% by weight lactic acid aqueous solution was measured using “F-kit glycerol” (manufactured by Roche Diagnostics) under the same conditions as in Example 11. As a result, the glycerol content in the 90% by weight lactic acid aqueous solution was measured. Was 72 ppm.
  • Example 12 Lactic acid polymerization test, evaluation of physical properties of polylactic acid
  • the 90% by weight aqueous lactic acid solution obtained in Example 11 was subjected to direct dehydration polycondensation, and the physical properties of the obtained polylactic acid were analyzed.
  • 150 g of lactic acid obtained in Example 11 was heated in a reaction vessel equipped with a stirrer at 800 Pa, 160 ° C. for 3.5 hours to obtain an oligomer.
  • 0.12 g of tin (II) acetate manufactured by Kanto Chemical Co., Ltd.
  • 0.33 g of methanesulfonic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • a polymer was obtained.
  • the prepolymer was then crystallized by heating in an oven at 120 ° C. for 2 hours.
  • the obtained prepolymer was pulverized using a hammer pulverizer and sieved to obtain a powder having an average particle diameter of 0.1 mm.
  • 150 g of prepolymer was taken and introduced into an oven connected with an oil rotary pump, and subjected to a heating and decompression treatment.
  • the pressure was 50 Pa
  • the heating temperature was 140 ° C .: 10 hours, 150 ° C .: 10 hours, and 160 ° C .: 20 hours.
  • the obtained polylactic acid was subjected to melting point analysis by GDSC (made by SII Nanotechnology Co., Ltd.) and thermal weight loss rate analysis by TG (made by SII Technology) under the following conditions.
  • the melting point of the polymerized polylactic acid is a value measured by a differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Co., Ltd.). The measurement conditions are 10 mg of a sample, under a nitrogen atmosphere, at a heating rate of 20 ° C./min. went.
  • thermogravimetric decrease rate of the polymerized polylactic acid was measured using a differential thermothermal gravimetric simultaneous measurement apparatus TG / DTA7200 (manufactured by SII Nanotechnology Inc.). The measurement conditions were a sample of 10 mg, a nitrogen atmosphere, 200 ° C. constant, and a heating time of 20 minutes. The melting point of polylactic acid obtained by direct polymerization of lactic acid was 167.3 ° C., and the thermal weight loss rate was 4.6%.
  • Comparative Example 3 Polymerization Test for Lactic Acid and Polymerization Evaluation for Polylactic Acid
  • Polylactic acid was polymerized and analyzed in the same procedure as in Example 12 except that the lactic acid obtained in Comparative Example 2 was used.
  • the resulting polylactic acid had a melting point of 165.4 ° C. and a thermal weight loss rate of 6.3%.
  • lactic acid with reduced glycerol produced according to the present invention is useful as a raw material for polylactic acid having an excellent melting point and thermal stability.
  • the lactic acid of the present invention is suitably used as a monomer raw material for polylactic acid, which is a biodegradable plastic, in addition to foods and pharmaceuticals.
  • the lactic acid of the present invention is suitably used as a raw material for polylactic acid having an excellent melting point and thermal stability.

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Abstract

[Problem] The present invention is a lactic acid production method involving a step for removing glycerol by means of an ion exchange resin from a lactic acid aqueous solution which contains glycerol as an impurity. By means of the present invention, lactic acid can easily and economically be separated from a lactic acid aqueous solution containing glycerol as an impurity.

Description

乳酸の製造方法Method for producing lactic acid
　本発明は、乳酸水溶液中の乳酸とグリセロールを分離することによる乳酸の製造方法に関する。 The present invention relates to a method for producing lactic acid by separating lactic acid and glycerol in an aqueous lactic acid solution.
　乳酸は、食品用、医薬用などといった用途の他に、生分解性プラスチックのモノマー原料として工業的用途にまで広く適用され、需要が増加している。２－ヒドロキシプロピオン酸、即ち乳酸は、微生物による発酵により生産されることが知られており、微生物はグルコースに代表される炭水化物を含有する基質を乳酸に変換する。乳酸は、カルボニルα位の炭素に結合している置換基の立体配座により、（Ｌ）－体および（Ｄ）－体の光学異性体に分類される。微生物発酵によれば、微生物を適宜選択することにより（Ｌ）－体または（Ｄ）－体の乳酸を選択的に、または（Ｌ）－体及び（Ｄ）－体の混合体（ラセミ体）の乳酸を生産することができる。 Lactic acid is widely applied to industrial uses as a monomer raw material for biodegradable plastics, in addition to uses such as food and medicine, and the demand is increasing. 2-Hydroxypropionic acid, that is, lactic acid, is known to be produced by fermentation by microorganisms, and microorganisms convert a substrate containing a carbohydrate represented by glucose into lactic acid. Lactic acid is classified into (L) -isomer and (D) -isomer optical isomers depending on the conformation of the substituent bonded to the carbon at the carbonyl α-position. According to microbial fermentation, by appropriately selecting a microorganism, (L) -form or (D) -form lactic acid is selectively selected or a mixture of (L) -form and (D) -form (racemic form). Of lactic acid.
　一般に、微生物発酵による乳酸の生産は培養液中にアルカリ性物質（例えば、水酸化カルシウム）を添加することで微生物発酵に最適なｐＨに保持されながら行われる。微生物発酵により生産された酸性物質である乳酸の多くは、アルカリ性物質が添加されることで、培養液中では乳酸塩（例えば、乳酸カルシウム）として存在している。乳酸をプラスチックのモノマーとして使用する場合、一般的に発酵終了後の培養液に酸性物質（例えば、硫酸）を添加することで得られるフリー体の乳酸が好ましく用いられる。ただし、微生物発酵により得られる乳酸発酵液中には、目的物である乳酸の他、有機酸とその塩、タンパク質、アミノ酸に加え、グリセロールなどの非イオン性の化合物が不純物として含まれており、乳酸をプラスチックのモノマーとして使用する場合、乳酸とこれらの不純物を分離する必要がある。 Generally, the production of lactic acid by microbial fermentation is performed while maintaining an optimum pH for microbial fermentation by adding an alkaline substance (for example, calcium hydroxide) to the culture solution. Most of lactic acid, which is an acidic substance produced by microbial fermentation, exists as a lactate salt (for example, calcium lactate) in the culture solution by adding an alkaline substance. When lactic acid is used as a monomer for plastics, generally free lactic acid obtained by adding an acidic substance (for example, sulfuric acid) to a culture solution after completion of fermentation is preferably used. However, in the lactic acid fermentation broth obtained by microbial fermentation, in addition to the target lactic acid, in addition to organic acids and their salts, proteins, amino acids, nonionic compounds such as glycerol are included as impurities, When lactic acid is used as a plastic monomer, it is necessary to separate lactic acid from these impurities.
　微生物発酵により得られる乳酸発酵液由来の乳酸水溶液から不純物を除去して乳酸を回収する方法として、例えば特許文献１には、乳酸水溶液をイオン交換処理してイオン成分を除去した後、処理液を蒸留する方法が記載されている。また、非イオン性の不純物の除去方法として、特許文献２には、乳酸水溶液に含まれる乳酸をイオン交換樹脂に吸着・溶出させることにより、該乳酸水溶液に含まれる不純物であるグリセロールを除去する方法が記載されている（ただし、特許文献２の実施例には乳酸をイオン交換樹脂に吸着・溶出させた例は記載されていない。）。 As a method of removing impurities from a lactic acid aqueous solution derived from a lactic acid fermentation broth obtained by microbial fermentation and recovering lactic acid, for example, Patent Document 1 discloses an ion exchange treatment of an aqueous lactic acid solution to remove ionic components, A method of distillation is described. Further, as a method for removing nonionic impurities, Patent Document 2 discloses a method for removing glycerol, which is an impurity contained in an aqueous lactic acid solution, by adsorbing and eluting lactic acid contained in the aqueous lactic acid solution to an ion exchange resin. (However, the example of Patent Document 2 does not describe an example in which lactic acid is adsorbed and eluted in an ion exchange resin.).
特表２００１－５０６２７４号公報JP-T-2001-506274 特開２００６－７５１３３号公報JP 2006-75133 A
　乳酸水溶液に含まれる不純物の中でも非イオン性のグリセロールと乳酸を分離する方法としては、前述のとおり乳酸水溶液に含まれる乳酸をイオン交換樹脂に吸着・溶出させることによって不純物であるグリセロールを除去する方法があるが、多量の乳酸をイオン交換樹脂に吸着させるためには大量のイオン交換樹脂が必要であるため、設備が大型化してしまうなどの課題が考えられた。 As a method for separating nonionic glycerol and lactic acid among impurities contained in an aqueous lactic acid solution, as described above, glycerol contained in the aqueous lactic acid solution is adsorbed and eluted by an ion exchange resin, thereby removing glycerol as an impurity. However, in order to adsorb a large amount of lactic acid on the ion exchange resin, a large amount of ion exchange resin is required, and thus problems such as an increase in equipment size have been considered.
　そこで本発明は、グリセロールを不純物として含有する乳酸水溶液から乳酸を分離する場合において、簡便かつ低コストにグリセロールを低減した乳酸を製造する方法を提供することを課題とする。 Therefore, an object of the present invention is to provide a method for producing lactic acid with reduced glycerol easily and at low cost when separating lactic acid from an aqueous lactic acid solution containing glycerol as an impurity.
　本発明者らは、上記課題を解決するため鋭意研究を行った結果、乳酸水溶液に含まれる非イオン性の不純物であるグリセロールをイオン交換樹脂に吸着させることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that glycerol, which is a nonionic impurity contained in an aqueous lactic acid solution, can be adsorbed on an ion exchange resin, and complete the present invention. It came to.
　すなわち、本発明は次の（１）～（６）から構成される。
（１）グリセロールを不純物として含有する乳酸水溶液からイオン交換樹脂によりグリセロールを除去する工程を含む、乳酸の製造方法。
（２）前記イオン交換樹脂が強酸性イオン交換樹脂である、（１）に記載の乳酸の製造方法。
（３）前記乳酸水溶液の乳酸濃度が２０重量％以上である、（１）または（２）に記載の乳酸の製造方法。
（４）イオン交換樹脂によりグリセロールを除去した乳酸水溶液を蒸留する工程を含む、（１）から（３）のいずれかに記載の乳酸の製造方法。
（５）（１）から（４）のいずれかに記載の乳酸の製造方法により得られる乳酸を原料とする、ポリ乳酸の製造方法。
（６）（１）から（４）のいずれかに記載の乳酸の製造方法により得られる乳酸を直接脱水重縮合する、ポリ乳酸の製造方法。 That is, the present invention comprises the following (1) to (6).
(1) A method for producing lactic acid, comprising a step of removing glycerol from an aqueous lactic acid solution containing glycerol as an impurity by an ion exchange resin.
(2) The method for producing lactic acid according to (1), wherein the ion exchange resin is a strongly acidic ion exchange resin.
(3) The method for producing lactic acid according to (1) or (2), wherein the lactic acid concentration of the lactic acid aqueous solution is 20% by weight or more.
(4) The method for producing lactic acid according to any one of (1) to (3), comprising a step of distilling a lactic acid aqueous solution from which glycerol has been removed by an ion exchange resin.
(5) A method for producing polylactic acid using lactic acid obtained by the method for producing lactic acid according to any one of (1) to (4) as a raw material.
(6) A method for producing polylactic acid, in which lactic acid obtained by the method for producing lactic acid according to any one of (1) to (4) is subjected to direct dehydration polycondensation.
　本発明により、乳酸水溶液中に不純物として含有するグリセロールを簡単な操作により効率的かつ低コストに低減することができ、融点、熱安定性に優れたポリ乳酸を製造するのに適した乳酸を製造することが可能となる。 According to the present invention, glycerol contained as an impurity in an aqueous lactic acid solution can be reduced efficiently and at low cost by a simple operation, and lactic acid suitable for producing polylactic acid having an excellent melting point and thermal stability is produced. It becomes possible to do.
　本発明の乳酸の製造方法は、グリセロールを不純物として含有する乳酸水溶液からイオン交換樹脂によりグリセロールを除去する工程を含むことを特徴としている。以下、本発明をより詳細に説明する。 The method for producing lactic acid according to the present invention includes a step of removing glycerol from an aqueous lactic acid solution containing glycerol as an impurity by an ion exchange resin. Hereinafter, the present invention will be described in more detail.
　本発明における「グリセロールを不純物として含有する乳酸水溶液」とは、乳酸を主成分として含み、不純物としてグリセロールを含む水溶液のことを意味する。グリセロールを不純物として含む限りは乳酸水溶液の由来は特に限定されず、有機合成によって得られた乳酸の水溶液であってもよく、微生物発酵により得られた乳酸発酵培養液そのものや、乳酸発酵培養液から複数の分離精製工程を経たものであってもよい。また、乳酸はイオン性物質であるため、グリセロールを不純物として含有する乳酸水溶液では、乳酸がフリー乳酸として存在する場合、乳酸塩として存在する場合またはそれらが平衡状態の場合があるが、後述の通り、乳酸がフリー体として存在している場合が本発明によるグリセロールの除去効果が高い。なお、乳酸水溶液に含まれる乳酸とグリセロールは、高速液体クロマトグラフィー（ＨＰＬＣ）によって定量することができる。 In the present invention, “an aqueous lactic acid solution containing glycerol as an impurity” means an aqueous solution containing lactic acid as a main component and glycerol as an impurity. The origin of the lactic acid aqueous solution is not particularly limited as long as it contains glycerol as an impurity, and may be an aqueous solution of lactic acid obtained by organic synthesis, from the lactic acid fermentation broth itself obtained by microbial fermentation, or from the lactic acid fermentation broth It may have undergone a plurality of separation and purification steps. Also, since lactic acid is an ionic substance, in lactic acid aqueous solution containing glycerol as an impurity, lactic acid may exist as free lactic acid, may exist as lactate salt, or they may be in an equilibrium state. The glycerol removal effect according to the present invention is high when lactic acid is present in a free form. The lactic acid and glycerol contained in the lactic acid aqueous solution can be quantified by high performance liquid chromatography (HPLC).
　イオン交換樹脂により乳酸水溶液に含まれるグリセロールを除去する工程では、上述の乳酸水溶液に含まれるグリセロールをイオン交換樹脂に吸着させることを特徴とする。イオン交換樹脂は合成樹脂の一種であり、分子構造の一部にイオン基として電離する構造を持つため、溶媒中のイオン成分とイオン交換作用を示す。従って、一般的にはイオン交換樹脂は溶液中のイオン成分を吸着する目的で使用されるが、乳酸水溶液という極性の高い溶液中の非イオン成分であるグリセロールがイオン交換樹脂に吸着することを見出したところに本発明の特徴がある。 In the step of removing glycerol contained in the lactic acid aqueous solution with the ion exchange resin, the glycerol contained in the lactic acid aqueous solution is adsorbed on the ion exchange resin. An ion exchange resin is a kind of synthetic resin and has a structure that ionizes as an ionic group in a part of its molecular structure, and thus exhibits an ion exchange action with an ion component in a solvent. Therefore, ion exchange resins are generally used for the purpose of adsorbing ionic components in solution, but glycerol, which is a nonionic component in a highly polar solution such as an aqueous lactic acid solution, is found adsorbed on ion exchange resins. There is a feature of the present invention.
　本発明において使用されるイオン交換樹脂としては特に限定はなく、一般に公知のものが使用でき、具体例として、“アンバーライト”（登録商標）（ダウ・ケミカル社製）、“ダイヤイオン”（登録商標）（三菱化学株式会社製）、“デュオライト”（登録商標）（ローム・アンド・ハース社製）などが市販されている。また、イオン交換樹脂は酸性（カチオン交換樹脂）、塩基性（アニオン交換樹脂）、またはこれらの塩型のいずれでも使用できるが、強酸性イオン交換樹脂がグリセロール吸着能に優れることから好ましく、Ｈ型の強酸性イオン交換樹脂が特に好ましい。なお、これらのイオン交換樹脂はいわゆるゲル型でもポーラス型の樹脂のいずれでも使用できる。強酸性イオン交換樹脂の具体例としては、三菱化学株式会社製の“ダイヤイオン”（登録商標）ＳＫ１Ｂ、ＳＫ１ＢＨ、ＳＫ１１０、ＳＫ１１２、ＰＫ２１６、ＰＫ２１６Ｈ、ＰＫ２１８、ＰＫ２２０、ＰＫ２２８、ＰＫ２２８Ｈ、ＵＢＫ０８、ＵＢＫ１０、ＵＢＫ１２、ＵＢＫ５３０、ＵＢＫ５５０、ＵＢＫ５３５、ＵＢＫ５５５、ダウ・ケミカル社製の“アンバーライト”（登録商標）ＩＲ１２０Ｂ　Ｎａ、ＩＲ１２０　Ｈ、ＩＲ１２４　Ｎａ、２００ＣＴ　Ｎａ、２００ＣＴ　Ｈ、２５２　Ｎａ、２５２　Ｎａ、ローム・アンド・ハース社製の“デュオライト”（登録商標）Ｃ２０Ｊ、Ｃ２０ＬＦ、Ｃ２５５ＬＦＨ、Ｃ２６Ａ、Ｃ２６ＴＲＨなどが挙げられる。 The ion exchange resin used in the present invention is not particularly limited, and generally known ion exchange resins can be used. Specific examples include “Amberlite” (registered trademark) (manufactured by Dow Chemical Co.), “Diaion” (registered) Trademark) (manufactured by Mitsubishi Chemical Corporation), “Duolite” (registered trademark) (manufactured by Rohm and Haas), and the like are commercially available. In addition, the ion exchange resin may be acidic (cation exchange resin), basic (anion exchange resin), or a salt form thereof, but a strong acid ion exchange resin is preferable because of its excellent glycerol adsorption ability, and H type. The strongly acidic ion exchange resin is particularly preferable. These ion exchange resins can be used in either a so-called gel type or porous type resin. Specific examples of strongly acidic ion exchange resins include “Diaion” (registered trademark) SK1B, SK1BH, SK110, SK112, PK216, PK216H, PK218, PK220, PK228, PK228H, UBK08, UBK10, UBK12 manufactured by Mitsubishi Chemical Corporation. , UBK530, UBK550, UBK535, UBK555, "Amberlite" (registered trademark) IR120BNa, IR120H, IR124Na, 200CTNa, 200CTH, 252Na, 252Na, Rohm and Haas, manufactured by Dow Chemical “Duolite” (registered trademark) C20J, C20LF, C255LFH, C26A, C26TRH, and the like are available.
　乳酸水溶液をイオン交換樹脂と接触させる方法としては、バッチ方式（攪拌槽式）およびカラム方式（固定床流通方式）のいずれの方式も採用することができるが、操作性が良いことから、カラム方式が好ましい。イオン交換樹脂カラムによるイオン交換処理の場合の乳酸水溶液の流速は特に制限はないが、通常、イオン交換樹脂の単位体積当たりの空間速度（ＳＶ）が０．１～２０ｈｒ－１となるようにすればよい。また、イオン交換樹脂カラムと乳酸水溶液の接触温度は特に限定はなく、常温で好適に使用できる。 As a method of bringing the aqueous lactic acid solution into contact with the ion exchange resin, either a batch method (stirring tank method) or a column method (fixed bed flow method) can be adopted. Is preferred. The flow rate of the aqueous lactic acid solution in the case of ion exchange treatment using an ion exchange resin column is not particularly limited, but it is usually set so that the space velocity (SV) per unit volume of the ion exchange resin is 0.1 to 20 hr −1. That's fine. The contact temperature between the ion exchange resin column and the lactic acid aqueous solution is not particularly limited and can be suitably used at room temperature.
　なお、グリセロール除去に使用したイオン交換樹脂は水による洗浄により再生することができる。通常、イオン成分を吸着したイオン交換樹脂の再生には酸、アルカリといった薬液による洗浄が必要であるが、非イオン成分であるグリセロールが吸着したイオン交換樹脂は極性の高い水で洗浄して再生できることから、イオン交換樹脂再生に必要な薬液コストを低減できる。樹脂再生に使用する水に特に限定はないが、イオン成分を多く含んだ水を使用した場合、該イオン成分によってイオン交換樹脂表面の官能基にイオン成分が吸着し、グリセロール吸着効果が低下するため、イオン交換水を用いた洗浄が好ましく適用できる。 In addition, the ion exchange resin used for glycerol removal can be regenerated by washing with water. Normally, regeneration of ion exchange resins that adsorb ionic components requires washing with chemicals such as acid and alkali, but ion exchange resins that adsorb glycerol, which is a nonionic component, can be regenerated by washing with highly polar water. Therefore, the chemical cost required for ion exchange resin regeneration can be reduced. The water used for resin regeneration is not particularly limited, but when water containing a large amount of ionic components is used, the ionic components are adsorbed on the functional groups on the surface of the ion exchange resin by the ionic components, and the glycerol adsorption effect is reduced. In addition, washing with ion-exchanged water can be preferably applied.
　イオン交換樹脂の工程に供する乳酸水溶液が微生物発酵による乳酸発酵培養液である場合、一般に培養時のｐＨ調整のためにアルカリ性物質が添加されるため、乳酸発酵培養液中の乳酸は乳酸塩として存在する。その場合、乳酸水溶液をイオン交換樹脂で処理する工程に先立つ前処理として、乳酸発酵培養液中の乳酸塩をフリー乳酸に変換することが好ましい。乳酸塩の具体例としては、乳酸リチウム、乳酸ナトリウム、乳酸カリウム、乳酸カルシウム、乳酸マグネシウム、乳酸アルミニウムまたは乳酸アンモニウムあるいはこれらの混合物が挙げられる。乳酸が乳酸塩として存在する乳酸発酵培養液をイオン交換樹脂で処理すると、乳酸塩をフリー乳酸とすることにイオン交換樹脂表面の官能基が優先的に使用され、それによりグリセロール吸着効果が低下するため、あらかじめフリー化した乳酸の水溶液をイオン交換樹脂で処理することで、グリセロール除去効果を高めることができる。 When the aqueous lactic acid solution used for the ion exchange resin process is a lactic acid fermentation broth by microbial fermentation, an alkaline substance is generally added to adjust the pH during the cultivation, so lactic acid in the lactic acid fermentation broth exists as a lactate. To do. In that case, it is preferable to convert lactate in the lactic acid fermentation broth into free lactic acid as a pretreatment prior to the step of treating the aqueous lactic acid solution with an ion exchange resin. Specific examples of the lactate include lithium lactate, sodium lactate, potassium lactate, calcium lactate, magnesium lactate, aluminum lactate, ammonium lactate, and mixtures thereof. When a lactic acid fermentation broth containing lactic acid as a lactate is treated with an ion exchange resin, the functional groups on the surface of the ion exchange resin are preferentially used to make the lactate free lactic acid, thereby reducing the glycerol adsorption effect. Therefore, the effect of removing glycerol can be enhanced by treating an aqueous solution of lactic acid that has been made free in advance with an ion exchange resin.
　乳酸塩からフリー乳酸を得る方法としては、酸性物質を添加する方法を採用できる。酸性物質は特に限定はなく、硫酸、塩酸、炭酸、リン酸、硝酸などを用いることができるが、後述の難溶性塩を形成する観点から硫酸を用いることが好ましい。乳酸塩水溶液に酸性物質を添加してフリーの乳酸水溶液に変換するとともに、乳酸塩の陽イオン成分を難溶性塩として除去することが好ましい。乳酸塩水溶液に酸性物質を添加し、該溶液中の陽イオン成分を難溶性塩として沈殿、濾別等により固液分離することで、乳酸塩由来の陽イオンが除去されたフリーの乳酸水溶液を得ることができる。なお、難溶性塩の固液分離の方法に特に限定はなく、定性濾紙による濾過や遠心分離など、当業者にとって公知の方法を適用できる。 As a method for obtaining free lactic acid from lactate, a method of adding an acidic substance can be employed. The acidic substance is not particularly limited, and sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid, nitric acid and the like can be used, but sulfuric acid is preferably used from the viewpoint of forming a hardly soluble salt described later. It is preferable to add an acidic substance to the aqueous lactate solution to convert it into a free lactic acid aqueous solution, and to remove the cationic component of the lactate as a hardly soluble salt. An acidic substance is added to the lactate aqueous solution, and the cation component in the solution is precipitated as a sparingly soluble salt and solid-liquid separated by filtration, etc. Obtainable. The method for solid-liquid separation of the hardly soluble salt is not particularly limited, and methods known to those skilled in the art, such as filtration with qualitative filter paper and centrifugation, can be applied.
　また、乳酸水溶液をイオン交換樹脂で処理する前に、溶存している塩を除去する工程に供してもよい。乳酸水溶液に溶存している塩を除去することで、イオン交換樹脂の工程でのグリセロール吸着効果を高めることができる。乳酸水溶液中の溶存塩の除去方法に特に限定はなく、イオン交換処理や膜濾過処理などが適用される。なお、ここでいうイオン交換処理とは、乳酸水溶液中のイオン成分（無機塩等）を除去するものであり、本発明でのイオン交換樹脂で乳酸水溶液の不純物であるグリセロールを除去することとは目的が異なる。 Further, before the aqueous lactic acid solution is treated with the ion exchange resin, it may be subjected to a step of removing dissolved salts. By removing the salt dissolved in the lactic acid aqueous solution, the glycerol adsorption effect in the ion exchange resin process can be enhanced. There is no particular limitation on the method for removing the dissolved salt in the lactic acid aqueous solution, and ion exchange treatment, membrane filtration treatment, and the like are applied. The ion exchange treatment here is to remove ionic components (inorganic salts, etc.) in the lactic acid aqueous solution, and to remove glycerol which is an impurity of the lactic acid aqueous solution with the ion exchange resin in the present invention. The purpose is different.
　膜濾過処理とは、乳酸を透過し、塩類を阻止する膜であれば特に限定はないが、ナノ濾過膜が好適である。ナノ濾過膜とは、ナノフィルター（ナノフィルトレーション膜、ＮＦ膜）とも呼ばれるものであり、「一価のイオンは透過し、二価のイオンを阻止する膜」と一般に定義される膜である。数ナノメートル程度の微小空隙を有していると考えられる膜で、主として、水中の微小粒子や分子、イオン、塩類等を阻止するために用いられる。ナノ濾過膜の素材としては、酢酸セルロース系ポリマー、ポリアミド、ポリエステル、ポリイミド、ビニルポリマーなどの高分子素材を使用することができるが、前記１種類の素材で構成される膜に限定されず、複数の膜素材を含む膜であってもよい。またその膜構造は、膜の少なくとも片面に緻密層を持ち、緻密層から膜内部あるいはもう片方の面に向けて徐々に大きな孔径の微細孔を有する非対称膜や、非対称膜の緻密層の上に別の素材で形成された非常に薄い機能層を有する複合膜のどちらでもよい。複合膜としては、例えば、特開昭６２－２０１６０６号公報に記載の、ポリスルホンを膜素材とする支持膜にポリアミドの機能層からなるナノ濾過膜を構成させた複合膜を用いることができる。 The membrane filtration treatment is not particularly limited as long as it is a membrane that permeates lactic acid and blocks salts, but a nanofiltration membrane is preferable. The nanofiltration membrane is also called a nanofilter (nanofiltration membrane, NF membrane), and is a membrane generally defined as “a membrane that transmits monovalent ions and blocks divalent ions”. . It is a membrane that is considered to have a minute gap of about several nanometers, and is mainly used to block minute particles, molecules, ions, salts, and the like in water. The material of the nanofiltration membrane can be a polymer material such as cellulose acetate polymer, polyamide, polyester, polyimide, vinyl polymer, but is not limited to the membrane composed of the one kind of material. The film | membrane containing these film | membrane raw materials may be sufficient. In addition, the membrane structure has a dense layer on at least one side of the membrane, and on the asymmetric membrane having fine pores gradually increasing from the dense layer to the inside of the membrane or the other side, or on the dense layer of the asymmetric membrane. Either a composite film having a very thin functional layer formed of another material may be used. As the composite membrane, for example, a composite membrane described in JP-A-62-201606 in which a nanofiltration membrane comprising a functional layer of polyamide is formed on a support membrane made of polysulfone as a membrane material can be used.
　ナノ濾過膜は一般にスパイラル型の膜エレメントとして使用されるが、本発明で用いるナノ濾過膜も、スパイラル型の膜エレメントとして好ましく使用される。好ましいナノ濾過膜エレメントの具体例としては、ＧＥ　Ｏｓｍｏｎｉｃｓ社製の“ＧＥｓｅｐａ”（登録商標）、アルファラバル社製のＮＦ９９またはＮＦ９９ＨＦ、フィルムテック社製のＮＦ－４５、ＮＦ－９０、ＮＦ－２００またはＮＦ－４００、東レ株式会社製のＵＴＣ６０を含む同社製ナノ濾過膜エレメントＳＵ－２１０、ＳＵ－２２０、ＳＵ－６００またはＳＵ－６１０が挙げられる。 The nanofiltration membrane is generally used as a spiral membrane element, but the nanofiltration membrane used in the present invention is also preferably used as a spiral membrane element. Specific examples of preferred nanofiltration membrane elements include “GEsepa” (registered trademark) manufactured by GE Osmonics, NF99 or NF99HF manufactured by Alfa Laval, NF-45, NF-90, NF-200 manufactured by Filmtech. NF-400, Nanofiltration membrane element SU-210, SU-220, SU-600 or SU-610 manufactured by Toray Industries Inc., including UTC60.
　イオン交換樹脂の工程に供される乳酸水溶液の乳酸濃度に特に制限はないが、乳酸水溶液の乳酸濃度が２０重量％未満の場合は、極性の高い水の影響により、イオン交換樹脂のグリセロール吸着を抑制してしまうため、濃縮操作により乳酸濃度を２０重量％以上に濃縮後にイオン交換樹脂で処理することが好ましい。また、乳酸水溶液の乳酸濃度が９０重量％を超える場合、乳酸水溶液の粘性が高くなり、イオン交換樹脂工程での乳酸水溶液の流動性や操作性が低下するため、乳酸濃度を９０重量％以下としてイオン交換樹脂処理することが好ましい。 The lactic acid concentration of the aqueous lactic acid solution used in the ion exchange resin process is not particularly limited. However, when the lactic acid concentration of the aqueous lactic acid solution is less than 20% by weight, the glycerol adsorption of the ion exchange resin is caused by the influence of highly polar water. Therefore, it is preferable to treat with an ion exchange resin after concentrating the lactic acid concentration to 20% by weight or more by a concentration operation. In addition, when the lactic acid concentration of the lactic acid aqueous solution exceeds 90% by weight, the viscosity of the lactic acid aqueous solution becomes high, and the fluidity and operability of the lactic acid aqueous solution in the ion exchange resin process are lowered. It is preferable to treat with an ion exchange resin.
　なお、乳酸水溶液を濃縮する方法は、エバポレーターに代表される濃縮装置で加熱、減圧により水を蒸発させたり、逆浸透膜により乳酸濃度を高めることができるが、濃縮に要するエネルギーを低減できることから、逆浸透膜による濃縮方法が好ましい。ここでいう逆浸透膜とは、非処理水の浸透圧以上の圧力差を駆動力にイオンや低分子量分子を濾別できる濾過膜である。なお、逆浸透膜による乳酸水溶液の濃縮では、乳酸水溶液中の水分を逆浸透膜の透過側に透過させることにより、非透過側に乳酸濃度を高めた乳酸水溶液を得ることができる。 In addition, the method of concentrating the lactic acid aqueous solution can evaporate water by heating and decompression with a concentrating device typified by an evaporator, or increase the lactic acid concentration by a reverse osmosis membrane, but can reduce the energy required for concentration. A concentration method using a reverse osmosis membrane is preferred. The reverse osmosis membrane here is a filtration membrane capable of filtering out ions and low molecular weight molecules by using a pressure difference equal to or higher than the osmotic pressure of non-treated water as a driving force. In addition, in the concentration of the lactic acid aqueous solution by the reverse osmosis membrane, the water in the lactic acid aqueous solution is allowed to permeate through the permeation side of the reverse osmosis membrane, thereby obtaining the lactic acid aqueous solution having an increased lactic acid concentration on the non-permeation side.
　乳酸水溶液の濃縮のための逆浸透膜の膜素材としては、一般に市販されている酢酸セルロース系ポリマー、ポリアミド、ポリエステル、ポリイミド、ビニルポリマーなどの高分子素材を使用することができるが、該１種類の素材で構成される膜に限定されず、複数の膜素材を含む膜であってもよい。またその膜構造は、膜の少なくとも片面に緻密層を持ち、緻密層から膜内部あるいはもう片方の面に向けて徐々に大きな孔径の微細孔を有する非対称膜や、非対称膜の緻密層の上に別の素材で形成された非常に薄い機能層を有する複合膜のどちらでもよい。また、逆浸透膜の膜形態としては、平膜型、スパイラル型、中空糸型など適宜の形態のものが使用できる。 As the membrane material of the reverse osmosis membrane for concentration of the lactic acid aqueous solution, commercially available polymer materials such as cellulose acetate polymer, polyamide, polyester, polyimide, vinyl polymer can be used. It is not limited to the film | membrane comprised by these materials, The film | membrane containing a some film | membrane material may be sufficient. In addition, the membrane structure has a dense layer on at least one side of the membrane, and on the asymmetric membrane having fine pores gradually increasing from the dense layer to the inside of the membrane or the other side, or on the dense layer of the asymmetric membrane. Either a composite film having a very thin functional layer formed of another material may be used. Moreover, as a membrane form of a reverse osmosis membrane, the thing of appropriate forms, such as a flat membrane type, a spiral type, and a hollow fiber type, can be used.
　逆浸透膜の具体例としては、東レ株式会社製のポリアミド系逆浸透膜ＵＴＣ－７０、ＳＵ－７１０、ＳＵ－７２０、ＳＵ－７２０Ｆ、ＳＵ－７１０Ｌ、ＳＵ－７２０Ｌ、ＳＵ－７２０ＬＦ、ＳＵ－７２０Ｒ、ＳＵ－７１０Ｐ、ＳＵ－７２０Ｐ、ＳＵ－８１０、ＳＵ－８２０、ＳＵ－８２０Ｌ、ＳＵ－８２０ＦＡ、ＳＵ－６１０、ＳＵ－６２０、ＴＭ８００、ＴＭ８００Ｃ、ＴＭ８００Ａ、ＴＭ８００Ｈ、ＴＭ８００Ｅ、ＴＭ８００Ｌ、東レ株式会社製の酢酸セルロース系逆浸透膜ＳＣ－Ｌ１００Ｒ、ＳＣ－Ｌ２００Ｒ、ＳＣ－１１００、ＳＣ－１２００、ＳＣ－２１００、ＳＣ－２２００、ＳＣ－３１００、ＳＣ－３２００、ＳＣ－８１００、ＳＣ－８２００、日東電工株式会社製のＮＴＲ－７５９ＨＲ、ＮＴＲ－７２９ＨＦ、ＮＴＲ－７０ＳＷＣ、ＥＳ１０－Ｄ、ＥＳ２０－Ｄ、ＥＳ２０－Ｕ、ＥＳ１５－Ｄ、ＥＳ１５－Ｕ、ＬＦ１０－Ｄ、アルファラバル製のＲＯ９８ｐＨｔ、ＲＯ９９、ＨＲ９８ＰＰ、ＣＥ４０４０Ｃ－３０Ｄ、ＮＦ９９、ＮＦ９９ＨＦ、ＧＥ製のＧＥ　Ｓｅｐａ、ＯＳＭＯ　ＢＥＶ　ＮＦ　Ｓｅｒｉｅｓ、ＨＬ　　Ｓｅｒｉｅｓ、Ｄｕｒａｓｌｉｃｋ　Ｓｅｒｉｅｓ、ＭＵＮＩ　ＮＦ　Ｓｅｒｉｅｓ、ＣＫ　Ｓｅｒｉｅｓ、ＤＫ　Ｓｅｒｉｅｓ、Ｓｅａｓｏｆｔ　Ｓｅｒｉｅｓ、Ｄｕｒａｔｈｅｒｍ　ＨＷＳ　Ｓｅｒｉｅｓ、ＫＯＣＨ製のＳｅｌＲＯ　Ｓｅｒｉｅｓ、Ｆｉｌｍｔｅｃ製のＢＷ３０－４０４０、ＴＷ３０－４０４０、ＸＬＥ－４０４０、ＬＰ－４０４０、ＬＥ－４０４０、ＳＷ３０－４０４０、ＳＷ３０ＨＲＬＥ－４０４０、ＮＦ４５、ＮＦ９０、ＮＦ２００、ＮＦ４００などが挙げられる。 Specific examples of the reverse osmosis membrane include polyamide reverse osmosis membrane UTC-70, SU-710, SU-720, SU-720F, SU-710L, SU-720L, SU-720LF, SU-720R manufactured by Toray Industries, Inc. , SU-710P, SU-720P, SU-810, SU-820, SU-820L, SU-820FA, SU-610, SU-620, TM800, TM800C, TM800A, TM800H, TM800E, TM800L, manufactured by Toray Industries, Inc. Cellulose acetate reverse osmosis membranes SC-L100R, SC-L200R, SC-1100, SC-1200, SC-2100, SC-2200, SC-3100, SC-3200, SC-8100, SC-8200, Nitto Denko Corporation NTR-759HR, NTR-729HF, NTR-7 SWC, ES10-D, ES20-D, ES20-U, ES15-D, ES15-U, LF10-D, Alfa Laval RO98pHt, RO99, HR98PP, CE4040C-30D, NF99, NF99HF, GE Sepa, OS40 BEV NF Series, HL Series, Duraslick Series, MUNI NF Series, CK Series, DK Series, Deratherm HWS Series, 40W made by 40W -4040, LE-4040, SW30-4040, SW30HRLE-4040, NF45, N 90, NF200, NF400 and the like.
　また、本発明ではイオン交換樹脂の工程で得られた乳酸水溶液をさらに蒸留する工程に供することで、グリセロールをより低減した高純度の乳酸が得られる。蒸留工程に供する乳酸水溶液の乳酸濃度に特に制限はなく、イオン交換樹脂処理で得られる乳酸水溶液をそのまま蒸留してもよく、さらにエバポレーターや前述の逆浸透膜による濃縮工程に供してから蒸留を行ってもよい。ただし、溶液中の乳酸濃度が低すぎると蒸留設備が大きくなり、濃度が高すぎるとオリゴマー化して収率が低下するおそれがあるため、５０～９５重量％、より好ましくは６０～９０重量％であれば好適に蒸留を行うことができる。また、蒸留工程は、１Ｐａ以上大気圧（常圧、約１０１ｋＰａ）以下の減圧下で行われる。１０Ｐａ以上３０ｋＰａ以下の減圧下で行えば、蒸留温度を低減できることからより好ましい。減圧下で行う場合の蒸留温度は、２０℃以上２００℃以下で行われるが、１８０℃以上で蒸留を行った場合、不純物の影響により、乳酸がラセミ化するおそれがあるため、５０℃以上１８０℃以下、より好ましくは６０℃以上１５０℃以下であれば、好適に乳酸の蒸留を行うことができる。なお、乳酸は構造上、脱水条件（加熱、減圧）によりオリゴマー化しやすいため、可能な限り滞留時間を低減させることが好ましい。したがって、蒸留装置として、落下フィルム蒸発装置、拭き取りフィルム蒸発装置などの薄膜蒸発装置を用いることで短時間の蒸留を達成できるため、乳酸の回収率を向上できることから好ましい。 In the present invention, the lactic acid aqueous solution obtained in the ion exchange resin step is further subjected to a distillation step, whereby high-purity lactic acid with further reduced glycerol can be obtained. There is no particular limitation on the lactic acid concentration of the aqueous lactic acid solution used for the distillation process, and the lactic acid aqueous solution obtained by the ion exchange resin treatment may be distilled as it is, and further subjected to the concentration step using an evaporator or the above-mentioned reverse osmosis membrane before the distillation. May be. However, if the concentration of lactic acid in the solution is too low, the distillation equipment becomes large, and if the concentration is too high, oligomerization may occur and the yield may decrease, so 50 to 95% by weight, more preferably 60 to 90% by weight. If there is, distillation can be suitably performed. The distillation step is performed under a reduced pressure of 1 Pa or more and atmospheric pressure (normal pressure, about 101 kPa) or less. It is more preferable to carry out under a reduced pressure of 10 Pa or more and 30 kPa or less because the distillation temperature can be reduced. The distillation temperature under reduced pressure is 20 ° C. or higher and 200 ° C. or lower. However, when distillation is performed at 180 ° C. or higher, lactic acid may be racemized due to the influence of impurities. The lactic acid can be suitably distilled at a temperature of ℃ or lower, more preferably 60 ℃ or higher and 150 ℃ or lower. Note that lactic acid is structurally easy to oligomerize under dehydrating conditions (heating, reduced pressure), and therefore it is preferable to reduce the residence time as much as possible. Therefore, since a short-time distillation can be achieved by using a thin film evaporator such as a falling film evaporator or a wiping film evaporator as the distillation apparatus, it is preferable because the recovery rate of lactic acid can be improved.
　前記乳酸を重合して得られるポリ乳酸には、Ｌ－乳酸単位またはＤ－乳酸単位のホモポリマーや、ポリ－Ｌ－乳酸単位からなるセグメントとポリ－Ｄ－乳酸単位からなるセグメントにより構成されるポリ乳酸ブロック共重合体や、乳酸以外の他のモノマーとの共重合体が含まれる。共重合体である場合、乳酸以外の他のモノマー単位としては、エチレングリコール、プロピレングリコール、ブタンジオール、ヘプタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、デカンジオール、１，４－シクロヘキサンジメタノール、ネオペンチルグリコール、グリセリン、ペンタエリスリトール、ビスフェノールＡ、ポリエチレングリコール、ポリプロピレングリコールおよびポリテトラメチレングリコールなどのグリコール化合物、シュウ酸、アジピン酸、セバシン酸、アゼライン酸、ドデカンジオン酸、マロン酸、グルタル酸、シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸、ビス（ｐ－カルボキシフェニル）メタン、アントラセンジカルボン酸、ジフェニルエーテルジカルボン酸、ナトリウムスルホイソフタル酸、テトラブチルホスホニウムイソフタル酸などのジカルボン酸、グリコール酸、ヒドロキシプロピオン酸、ヒドロキシ酪酸、ヒドロキシ吉相酸、ヒドロキシカプロン酸、ヒドロキシ安息香酸などのヒドロキシカルボン酸、カプロラクトン、バレロラクトン、プロピオラクトン、ウンデカラクトン、１，５－オキセパン－２－オンなどのラクトン類を挙げることができる。上記他の共重合成分の共重合量は、全単量体成分に対し、０～３０モル％であることが好ましく、０～１０モル％であることがより好ましい。 The polylactic acid obtained by polymerizing lactic acid is composed of homopolymers of L-lactic acid units or D-lactic acid units, segments composed of poly-L-lactic acid units, and segments composed of poly-D-lactic acid units. Polylactic acid block copolymers and copolymers with other monomers other than lactic acid are included. In the case of a copolymer, monomer units other than lactic acid include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neo Glycol compounds such as pentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid Acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, diphe Dicarboxylic acids such as ether dicarboxylic acid, sodium sulfoisophthalic acid, tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxy phacolic acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, caprolactone, valerolactone And lactones such as propiolactone, undecalactone, and 1,5-oxepan-2-one. The copolymerization amount of the other copolymerization components is preferably 0 to 30 mol%, more preferably 0 to 10 mol%, based on all monomer components.
　前記ポリ乳酸の製造方法は特に限定されず、一般のポリ乳酸の製造方法を利用することができる。具体的には、乳酸を原料として、一旦、環状２量体であるラクチドを生成せしめ、その後、開環重合を行う２段階のラクチド法と、当該原料を溶媒中で直接脱水重縮合を行う一段階の直接重合法などが知られており、いずれの製法を利用してもよい。 The method for producing the polylactic acid is not particularly limited, and a general method for producing polylactic acid can be used. Specifically, a lactide which is a cyclic dimer is produced once using lactic acid as a raw material, and then ring-opening polymerization is performed, and a direct dehydration polycondensation of the raw material in a solvent is performed. A direct polymerization method in stages is known, and any production method may be used.
　ラクチド法および直接重合法においては、重合反応に触媒を用いることにより、重合時間を短縮することができる。触媒としては、例えば、錫、亜鉛、鉛、チタン、ビスマス、ジルコニウム、ゲルマニウム、アンチモン、アルミニウムなどの金属及びその誘導体が挙げられる。誘導体としては、金属アルコキシド、カルボン酸塩、炭酸塩、酸化物、ハロゲン化物が好ましい。具体的には、塩化錫、酢酸錫、オクチル酸錫、塩化亜鉛、酸化鉛、炭酸鉛、塩化チタン、アルコキシチタン、酸化ゲルマニウム、酸化ジルコニウムなどが挙げられ、これらの中でも錫化合物が好ましく、酢酸錫またはオクチル酸錫がより好ましい。 In the lactide method and the direct polymerization method, the polymerization time can be shortened by using a catalyst for the polymerization reaction. Examples of the catalyst include metals such as tin, zinc, lead, titanium, bismuth, zirconium, germanium, antimony, and aluminum, and derivatives thereof. Derivatives are preferably metal alkoxides, carboxylates, carbonates, oxides and halides. Specific examples include tin chloride, tin acetate, tin octylate, zinc chloride, lead oxide, lead carbonate, titanium chloride, alkoxytitanium, germanium oxide, zirconium oxide, etc. Among these, tin compounds are preferred, and tin acetate Or tin octylate is more preferable.
　重合反応は、上記触媒の存在下、触媒種によっても異なるが通常１００～２００℃の温度で行うことができる。また、重合反応に伴って生成する水を除くために、重合反応は減圧条件下で行われることが望ましく、好ましくは７ｋＰａ以下、より好ましくは１．５ｋＰａ以下である。 The polymerization reaction can be usually performed at a temperature of 100 to 200 ° C. in the presence of the above catalyst, although it varies depending on the catalyst type. Moreover, in order to remove the water produced | generated with a polymerization reaction, it is desirable for a polymerization reaction to be performed under pressure reduction conditions, Preferably it is 7 kPa or less, More preferably, it is 1.5 kPa or less.
　また、重合反応時には水酸基またはアミノ基を分子内に２個以上含有する化合物を重合開始剤として用いてもよい。ここで、重合開始剤として用いる水酸基またはアミノ基を分子内に２個以上含有する化合物としては、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール、オクタンジオール、ネオペンチルグリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ソルビトール、ポリ（ビニルアルコール）、ポリ（ヒドロキシエチルメタクリレート）、ポリ（ヒドロキシプロピルメタクリレート）などの多価アルコール、エチレンジアミン、プロピレンジアミン、ブタンジアミン、ヘキサンジアミン、ジエチレントリアミン、メラミンなどの多価アミンなどが挙げられ、なかでも、多価アルコールがより好ましい。 In the polymerization reaction, a compound containing two or more hydroxyl groups or amino groups in the molecule may be used as the polymerization initiator. Here, as the compound containing two or more hydroxyl groups or amino groups in the molecule as a polymerization initiator, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, neopentyl glycol, diethylene glycol, triethylene glycol, Polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, poly (vinyl alcohol), poly (hydroxyethyl methacrylate), poly (hydroxypropyl methacrylate), Ethylenediamine, propylenediamine, butanediamine, hexanediamine, diethylenetriamine, melamine, etc. Amine and the like. Among these, polyhydric alcohols are more preferable.
　前記重合開始剤の添加量は、特に限定されるものではないが、使用する原料（Ｌ－乳酸、Ｄ－乳酸、Ｌ，Ｌ－ラクチドまたはＤ，Ｄ－ラクチド）１００重量部に対して０．００１～５重量部が好ましく、０．０１～３重量部がより好ましい。 The amount of the polymerization initiator to be added is not particularly limited, but is 0.1% with respect to 100 parts by weight of the raw material used (L-lactic acid, D-lactic acid, L, L-lactide or D, D-lactide). 001 to 5 parts by weight is preferable, and 0.01 to 3 parts by weight is more preferable.
　また、直接重合法によりポリ乳酸を製造する場合に使用する溶媒としては、重合に影響を及ぼさなければ特に制限は無く、水や有機溶媒を用いることができる。有機溶媒の場合、例えば、芳香族炭化水素類が挙げられる。芳香族炭化水素類としては、例えば、トルエン、キシレン、ナフタレン、クロロベンゼン、ジフェニルエーテルなどが挙げられる。また、直接重合法によりポリ乳酸を製造する場合、縮合反応で生成する水を系外に排出することにより、重合を促進することができる。系外に排出する方法としては、減圧条件下で重合を行うことが好ましく、具体的には、７ｋＰａ以下、より好ましくは１．５ｋＰａ以下である。 Also, the solvent used when producing polylactic acid by the direct polymerization method is not particularly limited as long as it does not affect the polymerization, and water or an organic solvent can be used. In the case of an organic solvent, for example, aromatic hydrocarbons can be mentioned. Examples of aromatic hydrocarbons include toluene, xylene, naphthalene, chlorobenzene, diphenyl ether, and the like. Moreover, when manufacturing polylactic acid by a direct polymerization method, superposition | polymerization can be accelerated | stimulated by discharging | emitting the water produced | generated by a condensation reaction out of a system. As a method of discharging out of the system, it is preferable to perform polymerization under reduced pressure conditions, specifically, 7 kPa or less, more preferably 1.5 kPa or less.
　以下、実施例を用いて本発明をより詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
　実施例１～４　イオン交換樹脂によるグリセロールの吸着除去試験
　９０重量％の乳酸水溶液（和光純薬工業株式会社製）１００ｇに純水３５０ｇを添加して２０重量％乳酸水溶液を調製し、１２０℃の油浴で５時間加熱還流して水溶液中の乳酸オリゴマーを加水分解し、乳酸モノマーの水溶液とした。続いて、ロータリーエバポレーターを用いて乳酸水溶液を濃縮後、グリセロールを乳酸に対して５重量％となるように添加して、グリセロールを含有する７５重量％乳酸水溶液を調製した。この乳酸水溶液２０ｇに対してそれぞれＨ型強酸性イオン交換樹脂“ダイヤイオン”（登録商標）ＳＫ１ＢＨ（三菱化学株式会社製）２ｇ（実施例１）、Ｎａ型強酸性イオン交換樹脂“ダイヤイオン”（登録商標）ＳＫ１Ｂ（三菱化学株式会社製）２ｇ（実施例２）、ＣＬ型強塩基性イオン交換樹脂“アンバーライト”（登録商標）ＩＲ４１０ＪＣＬ（ダウ・ケミカル社製）２ｇ（実施例３）、ＯＨ型弱塩基性イオン交換樹脂“ダイヤイオン”（登録商標）ＷＡ２０（三菱化学株式会社製）２ｇ（実施例４）を添加し、室温で２時間、３００ｒｐｍで攪拌した。イオン交換樹脂処理前後の乳酸水溶液中のグリセロール濃度を高速液体クロマトグラフィーで測定し、グリセロール吸着除去率を以下の式１の方法で算出した。
グリセロール吸着除去率（％）＝１００×（イオン交換樹脂処理前のグリセロール濃度（ｇ／Ｌ）－イオン交換樹脂処理後のグリセロール濃度（ｇ／Ｌ））／イオン交換樹脂処理前のグリセロール濃度（ｇ／Ｌ）・・・（式１）。 Examples 1 to 4 Adsorption / removal test of glycerol with ion exchange resin To 100 g of 90% by weight lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), 350 g of pure water was added to prepare a 20% by weight lactic acid aqueous solution at 120 ° C. The mixture was heated and refluxed in an oil bath for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution to obtain an aqueous solution of lactic acid monomer. Subsequently, after concentrating the aqueous lactic acid solution using a rotary evaporator, glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol. 20 g of this aqueous lactic acid solution is 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) (Example 1), Na-type strongly acidic ion exchange resin “Diaion” ( (Registered trademark) SK1B (manufactured by Mitsubishi Chemical Corporation) 2 g (Example 2), CL type strongly basic ion exchange resin “Amberlite” (registered trademark) IR410JCL (manufactured by Dow Chemical Co.) 2 g (Example 3), OH Type weakly basic ion exchange resin “Diaion” (registered trademark) WA20 (Mitsubishi Chemical Corporation) 2 g (Example 4) was added and stirred at room temperature for 2 hours at 300 rpm. The glycerol concentration in the aqueous lactic acid solution before and after the ion exchange resin treatment was measured by high performance liquid chromatography, and the glycerol adsorption removal rate was calculated by the method of the following formula 1.
Glycerol adsorption removal rate (%) = 100 × (glycerol concentration before ion exchange resin treatment (g / L) −glycerol concentration after ion exchange resin treatment (g / L)) / glycerol concentration before ion exchange resin treatment (g / L) (Formula 1).
　なお、乳酸水溶液中のグリセロール濃度は、高速液体クロマトグラフィー（株式会社島津製作所製）により以下の条件で測定した。結果を表１に示す。
カラム：ＳｈｏｄｅｘＮＨ２Ｐ－５０　４Ｅ（昭和電工株式会社製）、移動相：アセトニトリル：水＝３：１、流速：０．６ｍＬ／ｍｉｎ、検出方法：示差屈折率検出器（ＲＩ）、カラム温度：３０℃
　比較例１　活性炭によるグリセロール吸着除去試験
　９０重量％の乳酸水溶液（和光純薬工業株式会社製）１００ｇに純水３５０ｇを添加して２０重量％乳酸水溶液を調製し、１２０℃の油浴で５時間加熱還流して水溶液中の乳酸オリゴマーを加水分解し、乳酸モノマーの水溶液とした。続いて、ロータリーエバポレーターを用いて乳酸水溶液を濃縮後、グリセロールを乳酸に対して５重量％となるように添加して、グリセロールを含有する７５重量％乳酸水溶液を調製した。この乳酸水溶液２０ｇに対して活性炭白鷺Ａ（日本エンバイロケミカルズ株式会社製）０．１ｇを添加し、室温で２時間、３００ｒｐｍで攪拌した。続いて、定性濾紙Ｎｏ．２（アドバンテック製）で活性炭を濾別し、活性炭処理した乳酸水溶液を得た。活性炭処理によるグリセロール吸着除去率は実施例１～４と同様の手順で算出した。結果を表１に示す。 The glycerol concentration in the aqueous lactic acid solution was measured under the following conditions by high performance liquid chromatography (manufactured by Shimadzu Corporation). The results are shown in Table 1.
Column: ShodexNH2P-50 4E (manufactured by Showa Denko KK), mobile phase: acetonitrile: water = 3: 1, flow rate: 0.6 mL / min, detection method: differential refractive index detector (RI), column temperature: 30 ° C.
Comparative Example 1 Glycerol adsorption removal test with activated carbon 350 g of pure water was added to 100 g of 90 wt% lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 20 wt% lactic acid aqueous solution, and the oil bath at 120 ° C. for 5 hours The solution was heated to reflux to hydrolyze the lactic acid oligomer in the aqueous solution to obtain an aqueous solution of lactic acid monomer. Subsequently, after concentrating the aqueous lactic acid solution using a rotary evaporator, glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol. To 20 g of this lactic acid aqueous solution, 0.1 g of activated carbon Shirasagi A (manufactured by Nippon Enviro Chemicals) was added and stirred at room temperature for 2 hours at 300 rpm. Subsequently, qualitative filter paper No. The activated carbon was filtered off with No. 2 (manufactured by Advantech) to obtain an activated lactic acid aqueous solution. The glycerol adsorption removal rate by the activated carbon treatment was calculated in the same procedure as in Examples 1 to 4. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すとおり、グリセロールを含有する乳酸水溶液をイオン交換樹脂で処理することで、グリセロールを低減した乳酸水溶液が得られることが示され、特に強酸性イオン交換樹脂のグリセロール除去効果が高いことがわかった。 As shown in Table 1, it is shown that a lactic acid aqueous solution with reduced glycerol can be obtained by treating a lactic acid aqueous solution containing glycerol with an ion exchange resin, and that a strong acidic ion exchange resin has a particularly high glycerol removal effect. all right.
　実施例５～９　イオン交換樹脂によるグリセロール除去における乳酸濃度依存性試験
　９０重量％の乳酸水溶液（和光純薬工業株式会社製）１００ｇに純水３４５．５ｇ、グリセロール（和光純薬工業株式会社製）４．５ｇを添加して２０重量％乳酸水溶液（対乳酸グリセロール濃度５重量％）を調製し、１２０℃の油浴で５時間加熱還流して水溶液中の乳酸オリゴマーを加水分解し、乳酸モノマーの水溶液とした。続いて、ロータリーエバポレーターを用いて乳酸水溶液を９０重量％（実施例５）、７５重量％（実施例６）、５０重量％（実施例７）、２５重量％（実施例８）、１０重量％（実施例９）となるように濃縮した。それぞれの濃度の乳酸水溶液２０ｇに対してＨ型強酸性イオン交換樹脂“ダイヤイオン”（登録商標）ＳＫ１ＢＨ（三菱化学株式会社製）２ｇを添加し、室温で２時間、３００ｒｐｍで攪拌した。各サンプルにおけるグリセロール除去率は実施例１～４と同様の方法で算出した。結果は表２に示すとおりであり、乳酸濃度が高いほど、すなわち水分濃度が低いほどグリセロール吸着除去効果が高いことが示された。 Examples 5 to 9 Lactic acid concentration dependency test in glycerol removal by ion exchange resin 90% by weight of lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 100 g pure water 345.5 g, glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) 4.5 g was added to prepare a 20% by weight aqueous lactic acid solution (concentration of glycerol lactate of 5% by weight), and heated to reflux in an oil bath at 120 ° C. for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution. An aqueous solution was obtained. Subsequently, 90% by weight (Example 5), 75% by weight (Example 6), 50% by weight (Example 7), 25% by weight (Example 8), and 10% by weight of an aqueous lactic acid solution using a rotary evaporator. Concentrate to (Example 9). 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) was added to 20 g of each concentration of lactic acid aqueous solution, followed by stirring at 300 rpm for 2 hours at room temperature. The glycerol removal rate in each sample was calculated in the same manner as in Examples 1 to 4. The results are as shown in Table 2. It was shown that the higher the lactic acid concentration, that is, the lower the water concentration, the higher the glycerol adsorption removal effect.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１０　イオン交換水で再生したイオン交換樹脂によるグリセロール除去試験
　９０重量％の乳酸水溶液（和光純薬工業株式会社製）３００ｇに純水１０５０ｇを添加して２０重量％乳酸水溶液を調製し、１２０℃の油浴で５時間加熱還流して水溶液中の乳酸オリゴマーを加水分解し、乳酸モノマーの水溶液とした。続いて、ロータリーエバポレーターを用いて乳酸水溶液を濃縮後、グリセロールを乳酸に対して５重量％となるように添加して、グリセロールを含有する７５重量％乳酸水溶液を調製した。この乳酸水溶液２００ｇに対してＨ型強酸性イオン交換樹脂“ダイヤイオン”（登録商標）ＳＫ１ＢＨ（三菱化学株式会社製）２ｇを添加し、室温で２時間、３００ｒｐｍで攪拌した。次いで、吸引濾過によりイオン交換樹脂を濾別し、グリセロールが吸着したイオン交換樹脂を得た。回収したイオン交換樹脂に１０ｇのイオン交換水を添加し、室温で３０分間、３００ｒｐｍで攪拌し、デカンテーションによって洗浄液を除去する操作を２回繰り返した。洗浄したイオン交換樹脂に、乳酸に対して５重量％のグリセロールを含有する７５重量％乳酸水溶液２０ｇを新たに添加し、室温で２時間、３００ｒｐｍで攪拌した。イオン交換樹脂処理前後の乳酸水溶液中のグリセロール濃度を高速液体クロマトグラフィーで測定したところ、グリセロール除去率は４０．６％であった。 Example 10 Glycerol removal test using ion exchange resin regenerated with ion-exchanged water 1050 g of pure water was added to 300 g of 90% by weight lactic acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 20% by weight lactic acid aqueous solution. The mixture was heated and refluxed in an oil bath at 5 ° C. for 5 hours to hydrolyze the lactic acid oligomer in the aqueous solution to obtain an aqueous solution of the lactic acid monomer. Subsequently, after concentrating the aqueous lactic acid solution using a rotary evaporator, glycerol was added to 5% by weight with respect to lactic acid to prepare a 75% by weight aqueous lactic acid solution containing glycerol. 2 g of H-type strongly acidic ion exchange resin “Diaion” (registered trademark) SK1BH (manufactured by Mitsubishi Chemical Corporation) was added to 200 g of this aqueous lactic acid solution, and the mixture was stirred at 300 rpm for 2 hours at room temperature. Subsequently, the ion exchange resin was separated by suction filtration to obtain an ion exchange resin adsorbed with glycerol. An operation of adding 10 g of ion-exchanged water to the collected ion-exchange resin, stirring at 300 rpm for 30 minutes at room temperature, and removing the cleaning solution by decantation was repeated twice. 20 g of a 75% by weight lactic acid aqueous solution containing 5% by weight of glycerol with respect to lactic acid was newly added to the washed ion exchange resin, and the mixture was stirred at 300 rpm for 2 hours at room temperature. When the glycerol concentration in the aqueous lactic acid solution before and after the ion exchange resin treatment was measured by high performance liquid chromatography, the glycerol removal rate was 40.6%.
　参考例１　イオン交換樹脂によるグリセロール除去試験（イオン交換水による再生なし）
　イオン交換水による洗浄を行わなかった以外は実施例１０と同様の手順でグリセロールの除去試験を実施した。イオン交換樹脂処理によるグリセロール除去率は４．７％であった。 Reference Example 1 Glycerol removal test with ion exchange resin (no regeneration with ion exchange water)
A glycerol removal test was performed in the same manner as in Example 10, except that no washing with ion-exchanged water was performed. The glycerol removal rate by the ion exchange resin treatment was 4.7%.
　実施例１０、参考例１の結果から、グリセロールが吸着したイオン交換樹脂をイオン交換水で洗浄することで、イオン交換樹脂の再生が可能であることが示された。 From the results of Example 10 and Reference Example 1, it was shown that the ion exchange resin can be regenerated by washing the ion exchange resin adsorbed with glycerol with ion exchange water.
　参考例２　バッチ発酵による乳酸の製造
　微生物を用いた発酵形態として最も典型的なバッチ発酵を行い、その乳酸生産性を評価した。表１に示す乳酸発酵培地を用い、バッチ発酵試験を行った。該培地は高圧蒸気滅菌（１２１℃、１５分）して用いた。微生物としてＷＯ２００９／００４９２２号に記載のＬ－乳酸発酵酵母ＳＷ－１株を用い、生産物である乳酸の濃度の評価には、以下に示したＨＰＬＣを用いて評価した。
カラム：Ｓｈｉｍ－Ｐａｃｋ　ＳＰＲ－Ｈ（株式会社島津製作所製）、移動相：５ｍＭ　ｐ－トルエンスルホン酸（流速０．８ｍＬ／ｍｉｎ）、反応液：５ｍＭ　ｐ－トルエンスルホン酸、２０ｍＭ　ビストリス、０．１ｍＭ　ＥＤＴＡ・２Ｎａ（流速０．８ｍＬ／ｍｉｎ）、検出方法：電気伝導度、温度：４５℃。 Reference Example 2 Production of lactic acid by batch fermentation The most typical batch fermentation was performed as a fermentation form using microorganisms, and the lactic acid productivity was evaluated. A batch fermentation test was conducted using the lactic acid fermentation medium shown in Table 1. The medium was used after autoclaving (121 ° C., 15 minutes). The L-lactic acid fermenting yeast strain SW-1 described in WO2009 / 004922 was used as a microorganism, and the concentration of lactic acid as a product was evaluated using the HPLC shown below.
Column: Shim-Pack SPR-H (manufactured by Shimadzu Corporation), mobile phase: 5 mM p-toluenesulfonic acid (flow rate 0.8 mL / min), reaction solution: 5 mM p-toluenesulfonic acid, 20 mM Bistris, 0.1 mM EDTA · 2Na (flow rate 0.8 mL / min), detection method: electrical conductivity, temperature: 45 ° C.
　参考例２の運転条件を以下に示す。
反応槽容量（乳酸発酵培地量）：２（Ｌ）、　温度調整：３０（℃）、反応槽通気量：０．２（Ｌ／ｍｉｎ）、反応槽攪拌速度：４００（ｒｐｍ）、ｐＨ調整：１Ｎ　水酸化カルシウムによりｐＨ５に調整。 The operating conditions of Reference Example 2 are shown below.
Reaction tank capacity (lactic acid fermentation medium amount): 2 (L), temperature adjustment: 30 (° C.), reaction tank aeration rate: 0.2 (L / min), reaction tank stirring speed: 400 (rpm), pH adjustment: Adjust to pH 5 with 1N calcium hydroxide.
　まず、ＳＷ－１株を試験管で５ｍｌの乳酸発酵培地で一晩振とう培養した（前々培養）。前々培養液を新鮮な乳酸発酵培地１００ｍｌに植菌し５００ｍｌ容坂口フラスコで２４時間振とう培養した（前培養）。温度調整、ｐＨ調整を行い、発酵培養を行った。この時の菌体増殖量は、６００ｎｍでの吸光度で１５であった。得られた乳酸発酵液（乳酸濃度３０ｇ／Ｌ、グリセロール濃度１ｇ／Ｌ）を以下の実施例で使用した。 First, the SW-1 strain was cultured overnight in a test tube with 5 ml of lactic acid fermentation medium (pre-culture). The culture solution was inoculated into 100 ml of fresh lactic acid fermentation medium and cultured with shaking in a 500 ml Sakaguchi flask for 24 hours (pre-culture). Temperature adjustment and pH adjustment were performed, and fermentation culture was performed. The amount of bacterial cell growth at this time was 15 in terms of absorbance at 600 nm. The resulting lactic acid fermentation broth (lactic acid concentration 30 g / L, glycerol concentration 1 g / L) was used in the following examples.
　実施例１１　乳酸発酵液を原料とした乳酸の製造例
　（酸性物質添加によるフリー乳酸の取得）
　参考例２で得られた培養液４０Ｌを攪拌しながら濃硫酸（和光純薬工業株式会社製）をｐＨ２．５になるまで滴下し、析出した硫酸カルシウムを定性濾紙Ｎｏ．２（アドバンテック製）を用いて濾別し、濾液を回収した。 Example 11 Example of production of lactic acid using lactic acid fermentation broth as raw material (Acquisition of free lactic acid by addition of acidic substance)
Concentrated sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to pH 2.5 while stirring 40 L of the culture solution obtained in Reference Example 2, and the precipitated calcium sulfate was added to qualitative filter paper No. 2 (manufactured by Advantech), and the filtrate was recovered.
　（ナノ濾過膜による濾過）
　濾液として回収した乳酸水溶液をナノ濾過膜モジュールＳＵ－６１０（東レ株式会社製）を用いて、操作圧力２．０ＭＰａで濾過し、透過液を回収した。 (Filtration with nanofiltration membrane)
The lactic acid aqueous solution recovered as the filtrate was filtered at an operating pressure of 2.0 MPa using a nanofiltration membrane module SU-610 (manufactured by Toray Industries, Inc.), and the permeate was recovered.
　（乳酸水溶液の濃縮）
　ナノ濾過膜透過液を逆浸透膜モジュールＳＵ－８１０（東レ株式会社製）を用いて濃縮し、さらに、ロータリーエバポレーター（東京理化器械株式会社製）を用いて、減圧下（５０ｈＰａ）で水を蒸発させて濃縮し、７５％乳酸水溶液を得た。グリセロールの濃度を実施例１と同様に高速液体クロマトグラフィーで分析した結果、乳酸に対するグリセロール濃度は２．０重量％であった。 (Concentration of lactic acid aqueous solution)
The nanofiltration membrane permeate is concentrated using a reverse osmosis membrane module SU-810 (manufactured by Toray Industries, Inc.), and the water is evaporated under reduced pressure (50 hPa) using a rotary evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.). And concentrated to obtain a 75% aqueous lactic acid solution. The concentration of glycerol was analyzed by high performance liquid chromatography in the same manner as in Example 1. As a result, the glycerol concentration relative to lactic acid was 2.0% by weight.
　（イオン交換樹脂処理によるグリセロールの吸着除去）
　濃縮した乳酸水溶液５００ｍＬをあらかじめＨ型に調製した強酸性陽イオン交換樹脂“ダイヤイオン”（登録商標）ＳＫ１Ｂ（三菱化学株式会社製）２５ｍＬを充填したカラムに２ＳＶ／ｈで供給し、流出液を回収した。イオン交換樹脂処理前後の乳酸水溶液中のグリセロールの濃度を参考例２と同様の条件で高速液体クロマトグラフィー（株式会社島津製作所製）を用いて測定した結果、乳酸に対するグリセロール濃度は１．２重量％まで減少した。以上の結果から、イオン交換樹脂で処理することで、グリセロールを効率的に低減できることがわかった。 (Adsorption removal of glycerol by ion exchange resin treatment)
A concentrated acidic lactic acid aqueous solution 500 mL was supplied to a column packed with 25 mL of a strongly acidic cation exchange resin “Diaion” (registered trademark) SK1B (manufactured by Mitsubishi Chemical Co., Ltd.) prepared in H form at 2 SV / h. It was collected. The concentration of glycerol in the aqueous lactic acid solution before and after the ion exchange resin treatment was measured using high performance liquid chromatography (manufactured by Shimadzu Corporation) under the same conditions as in Reference Example 2. As a result, the glycerol concentration relative to lactic acid was 1.2% by weight. Decreased to. From the above results, it was found that glycerol can be efficiently reduced by treatment with an ion exchange resin.
　（減圧蒸留）
　イオン交換樹脂で処理した乳酸水溶液２００ｇを１３３Ｐａ、１３０℃で減圧蒸留し、乳酸１５６ｇを得た。得られた乳酸に純水を添加して、９０重量％乳酸水溶液とした。９０重量％乳酸水溶液中のグリセロール濃度は“Ｆ－キット　グリセロール”（ロシュ・ダイアグノスティクス社製）を用いて測定した。その結果、９０重量％乳酸水溶液中のグリセロール含有量は１７ｐｐｍであった。 (Distilled under reduced pressure)
200 g of lactic acid aqueous solution treated with an ion exchange resin was distilled under reduced pressure at 133 Pa and 130 ° C. to obtain 156 g of lactic acid. Pure water was added to the obtained lactic acid to prepare a 90 wt% lactic acid aqueous solution. The glycerol concentration in the 90% by weight lactic acid aqueous solution was measured using “F-kit glycerol” (manufactured by Roche Diagnostics). As a result, the glycerol content in the 90% by weight lactic acid aqueous solution was 17 ppm.
　比較例２　乳酸発酵液を原料とした乳酸の製造例
　イオン交換樹脂処理によるグリセロールの吸着除去を行わなかった以外は、実施例１１と同様の手順で乳酸を製造し、減圧蒸留の結果、乳酸１４６ｇを得た。得られた乳酸に水を添加して、９０重量％乳酸水溶液とした。９０重量％乳酸水溶液中のグリセロール濃度は実施例１１と同様の条件で“Ｆ－キット　グリセロール”（ロシュ・ダイアグノスティクス社製）を用いて測定した結果、９０重量％乳酸水溶液中のグリセロール含有量は７２ｐｐｍであった。 Comparative Example 2 Lactic acid production example using lactic acid fermentation broth as raw material Lactic acid was produced in the same procedure as in Example 11 except that glycerol was not removed by adsorption by ion exchange resin treatment. Got. Water was added to the obtained lactic acid to prepare a 90% by weight aqueous lactic acid solution. The glycerol concentration in the 90% by weight lactic acid aqueous solution was measured using “F-kit glycerol” (manufactured by Roche Diagnostics) under the same conditions as in Example 11. As a result, the glycerol content in the 90% by weight lactic acid aqueous solution was measured. Was 72 ppm.
　実施例１２　乳酸の重合試験、ポリ乳酸の物性評価
　実施例１１で得た９０重量％乳酸水溶液を直接脱水重縮合し、得られたポリ乳酸の物性を分析した。実施例１１で得られた乳酸１５０ｇを、それぞれ撹拌装置のついた反応容器中で、８００Ｐａ、１６０℃、３．５時間加熱し、オリゴマーを得た。次いで、酢酸錫（ＩＩ）（関東化学株式会社製）０．１２ｇ、メタンスルホン酸（和光純薬工業株式会社製）０．３３ｇをオリゴマーに添加し、５００Ｐａ、１８０℃、７時間加熱し、プレポリマーを得た。次いで、プレポリマーをオーブンで１２０℃、２時間加熱して結晶化した。得られたプレポリマーを、ハンマー粉砕機を用いて粉砕し、ふるいにかけて平均粒子径０．１ｍｍの大きさの粉体を得た。固相重合工程では、１５０ｇのプレポリマーを取り、油回転ポンプを接続したオーブンに導入して、加熱減圧処理を行った。圧力は５０Ｐａ、加熱温度は１４０℃：１０時間、１５０℃：１０時間、１６０℃：２０時間とした。得られたポリ乳酸は以下の条件でＧＤＳＣ（エスアイアイ・ナノテクノロジー株式会社製）による融点分析、ＴＧ（エスアイアイ・テクノロジー製）による熱重量減少率分析を行った。 Example 12 Lactic acid polymerization test, evaluation of physical properties of polylactic acid The 90% by weight aqueous lactic acid solution obtained in Example 11 was subjected to direct dehydration polycondensation, and the physical properties of the obtained polylactic acid were analyzed. 150 g of lactic acid obtained in Example 11 was heated in a reaction vessel equipped with a stirrer at 800 Pa, 160 ° C. for 3.5 hours to obtain an oligomer. Next, 0.12 g of tin (II) acetate (manufactured by Kanto Chemical Co., Ltd.) and 0.33 g of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) are added to the oligomer, heated at 500 Pa, 180 ° C. for 7 hours, A polymer was obtained. The prepolymer was then crystallized by heating in an oven at 120 ° C. for 2 hours. The obtained prepolymer was pulverized using a hammer pulverizer and sieved to obtain a powder having an average particle diameter of 0.1 mm. In the solid phase polymerization step, 150 g of prepolymer was taken and introduced into an oven connected with an oil rotary pump, and subjected to a heating and decompression treatment. The pressure was 50 Pa, and the heating temperature was 140 ° C .: 10 hours, 150 ° C .: 10 hours, and 160 ° C .: 20 hours. The obtained polylactic acid was subjected to melting point analysis by GDSC (made by SII Nanotechnology Co., Ltd.) and thermal weight loss rate analysis by TG (made by SII Technology) under the following conditions.
　（ポリ乳酸の融点分析）
　重合したポリ乳酸の融点は、示差走査型熱量計ＤＳＣ７０２０（エスアイアイ・ナノテクノロジー株式会社製）により測定した値であり、測定条件は、試料１０ｍｇ、窒素雰囲気下、昇温速度２０℃／分で行った。 (Melting point analysis of polylactic acid)
The melting point of the polymerized polylactic acid is a value measured by a differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Co., Ltd.). The measurement conditions are 10 mg of a sample, under a nitrogen atmosphere, at a heating rate of 20 ° C./min. went.
　（ポリ乳酸の熱重量減少率分析）
　重合したポリ乳酸の熱重量減少率は、示差熱熱重量同時測定装置ＴＧ／ＤＴＡ７２００（エスアイアイ・ナノテクノロジー株式会社製）を用いて測定した。測定条件は、試料１０ｍｇ、窒素雰囲気下、２００℃一定、加熱時間２０分とした。乳酸の直接重合により得られたポリ乳酸の融点は１６７．３℃、熱重量減少率は４．６％であった。 (Thermal weight reduction rate analysis of polylactic acid)
The thermogravimetric decrease rate of the polymerized polylactic acid was measured using a differential thermothermal gravimetric simultaneous measurement apparatus TG / DTA7200 (manufactured by SII Nanotechnology Inc.). The measurement conditions were a sample of 10 mg, a nitrogen atmosphere, 200 ° C. constant, and a heating time of 20 minutes. The melting point of polylactic acid obtained by direct polymerization of lactic acid was 167.3 ° C., and the thermal weight loss rate was 4.6%.
　比較例３　乳酸の重合試験、ポリ乳酸の重合評価
　比較例２で得た乳酸を用いた以外は実施例１２と同様の手順でポリ乳酸を重合、分析した。得られたポリ乳酸の融点は１６５．４℃、熱重量減少率は６．３％であった。 Comparative Example 3 Polymerization Test for Lactic Acid and Polymerization Evaluation for Polylactic Acid Polylactic acid was polymerized and analyzed in the same procedure as in Example 12 except that the lactic acid obtained in Comparative Example 2 was used. The resulting polylactic acid had a melting point of 165.4 ° C. and a thermal weight loss rate of 6.3%.
　以上の結果より、本発明によって製造されたグリセロールを低減した乳酸は、融点や熱安定性に優れたポリ乳酸の原料として有用であることが示された。 From the above results, it was shown that lactic acid with reduced glycerol produced according to the present invention is useful as a raw material for polylactic acid having an excellent melting point and thermal stability.
　本発明の乳酸は、食品、医薬品のほか、生分解性プラスチックであるポリ乳酸のモノマー原料として好適に用いられる。また、本発明の乳酸は、融点、熱安定性に優れたポリ乳酸の原料として好適に用いられる。 The lactic acid of the present invention is suitably used as a monomer raw material for polylactic acid, which is a biodegradable plastic, in addition to foods and pharmaceuticals. The lactic acid of the present invention is suitably used as a raw material for polylactic acid having an excellent melting point and thermal stability.

Claims (6)

  1. 　グリセロールを不純物として含有する乳酸水溶液からイオン交換樹脂によりグリセロールを除去する工程を含む、乳酸の製造方法。 A method for producing lactic acid, comprising a step of removing glycerol from an aqueous lactic acid solution containing glycerol as an impurity by an ion exchange resin.
  2. 　前記イオン交換樹脂が強酸性イオン交換樹脂である、請求項１に記載の乳酸の製造方法。 The method for producing lactic acid according to claim 1, wherein the ion exchange resin is a strongly acidic ion exchange resin.
  3. 　前記乳酸水溶液の乳酸濃度が２０重量％以上である、請求項１または２に記載の乳酸の製造方法。 The method for producing lactic acid according to claim 1 or 2, wherein the lactic acid concentration of the lactic acid aqueous solution is 20% by weight or more.
  4. 　イオン交換樹脂によりグリセロールを除去した乳酸水溶液を蒸留する工程を含む、請求項１から３のいずれかに記載の乳酸の製造方法。 The method for producing lactic acid according to any one of claims 1 to 3, comprising a step of distilling a lactic acid aqueous solution from which glycerol has been removed by an ion exchange resin.
  5. 　請求項１から４のいずれかに記載の乳酸の製造方法により得られる乳酸を原料とする、ポリ乳酸の製造方法。 A method for producing polylactic acid using lactic acid obtained by the method for producing lactic acid according to any one of claims 1 to 4 as a raw material.
  6. 　請求項１から４のいずれかに記載の乳酸の製造方法により得られる乳酸を直接脱水重縮合する、ポリ乳酸の製造方法。 A method for producing polylactic acid, in which lactic acid obtained by the method for producing lactic acid according to any one of claims 1 to 4 is subjected to direct dehydration polycondensation.
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